Compositions for Golf Equipment

ABSTRACT

A golf ball comprising a core, an inner cover layer, and an outer cover layer, the outer cover layer being formed from a polyurea including a prepolymer and an amine curative. The prepolymer is formed from an aliphatic isocyanate and a secondary polyamine polyether having a formula: 
     
       
         
         
             
             
         
       
         
         where x=1-70; R 1  and R 2  each independently=a C 1-20  alkyl group, phenyl, or a mixture thereof; and R 3 ═H, CH 3 , or a mixture thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.11/940,412, filed Nov. 15, 2007, which is a continuation of co-pendingU.S. patent application Ser. No. 11/461,617, filed Aug. 1, 2006, whichis a continuation of U.S. Pat. No. 7,105,623, filed Jun. 2, 2004, whichis a continuation-in-part of U.S. patent application Ser. No.10/407,641, filed Apr. 4, 2003, now U.S. Pat. No. 6,861,492; acontinuation-in-part of U.S. patent application Ser. No. 10/434,738,filed May 9, 2003, now U.S. Pat. No. 6,989,431; a continuation-in-partof U.S. patent application Ser. No. 10/434,739, filed May 9, 2003, nowU.S. Pat. No. 6,949,617; a continuation-in-part of U.S. patentapplication Ser. No. 10/619,313, filed Jul. 14, 2003, now U.S. Pat. No.6,903,178; and a continuation-in-part of U.S. patent application Ser.No. 10/409,144, filed Apr. 9, 2003, now U.S. Pat. No. 6,958,379, whichis a continuation-in-part of U.S. patent application Ser. No.10/228,311, filed Aug. 27, 2002, now U.S. Pat. No. 6,835,794.

FIELD OF THE INVENTION

This application is directed to materials for golf ball layers and, inparticular, a polyurea-based material that is suited for golf ball coverlayers, more specifically outer cover layers.

SUMMARY OF THE INVENTION

The present invention is directed to a golf ball comprising a core, aninner cover layer, and an outer cover layer. The outer cover layer isformed from a polyurea material comprising a prepolymer and a curative.The prepolymer consists of an aliphatic isocyanate mixture comprisingdimerized uretdione of HDI and trimerized isocyanurate of HDI and afirst amount of modified polyoxypropylene diamine having a formula:

where x=1-70; R₁ and R₂ each independently=a C₁₋₂₀ alkyl group, phenyl,or a mixture thereof; and R₃═H, CH₃, or a mixture thereof. Nocaprolactone is present in the prepolymer. The curative is a mixture of3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine.Optionally, the aliphatic isocyanate mixture further includes thetrimerized biuret of HDI. To assure that the polyurea does not containany substantive polyurethane linkages, the modified polyoxypropylenediamine ideally does not contain an —OH group. The isocyanate mixturetypically has 6% free isocyanate to 9.5% free isocyanate.

In one embodiment, the core is a dual core and includes a solid centerand an outer core layer. The center preferably has an outer diameter of0.095 inches to 1.1 inches. The core, whether single or dual core,typically has an Atti compression of 75 or less. The outer cover layerhas a material hardness of 70 Shore C to 80 Shore C and a hardness, asmeasured directly on the golf ball, of 40 Shore D to 55 Shore D, whichis not inherent and is more a function of layer thickness and thehardness of the underlying layer. In a preferred embodiment, the outercover layer has a first hardness and the inner cover layer has a secondhardness, and a ratio of the first to second hardness is 0.8 to 0.7.

In another embodiment, the outer cover layer has a thickness of 0.025inches to 0.04 inches. The inner cover layer generally has a thicknessof 0.01 inches to 0.045 inches, more preferably 0.025 inches to 0.035inches. In another embodiment, the core has an outer diameter of 1.5inches to 1.6 inches.

The present invention is also directed to a golf ball consisting of acore and an outer cover layer. The outer cover layer is formed from apolyurea material including a prepolymer and a curative. The prepolymerconsists of an aliphatic isocyanate mixture including a dimerizeduretdione of HDI and trimerized isocyanurate of HDI (or, optionally, atrimerized biuret of HDI) and a modified polyoxypropylene diamine. Thecurative includes a mixture of 3,5-diethyl-2,4-toluenediamine and3,5-diethyl-2,6-toluenediamine. No caprolactone is present in theprepolymer and to help ensure that no substantive urethane linkages arein the polyurea, the modified polyoxypropylene diamine preferably doesnot contain an —OH group.

In one embodiment, the core is a dual core and includes a solid centerand an outer core layer. In another embodiment, the golf ball furtherincludes an inner cover layer disposed between the outer core layer andthe outer cover layer, the inner cover layer having a thickness of 0.02inches to 0.04 inches. The golf ball preferably has an Atti compressionof 95 to 120. In an alternative embodiment, the golf ball furtherincludes an inner cover layer disposed between the core and the outercover layer, the inner cover layer and outer cover layer each having athickness of 0.01 inches to 0.045 inches.

DETAILED DESCRIPTION OF THE INVENTION

The present disclosure relates to golf equipment such as golf balls,golf clubs (drivers, putters, woods, irons, and wedges, including headsand shafts thereof), golf shoes, golf gloves, golf bags, or the likethat comprise novel polyurethane, polyurea, and/orpoly(urethane-co-urea) compositions. The components of the compositionscan be saturated, i.e., substantially free of double or triplecarbon-carbon bonds or aromatic groups, to produce light stablecompositions. Components that are unsaturated or partially saturated canalso be used.

The golf ball can comprise at least one thermoplastic, thermoset,castable, or millable material formed from a composition comprising atleast one poly(urethane-co-urea) prepolymer and at least one curative.The poly(urethane-co-urea) prepolymer can be formed at least in partfrom at least one aminoalcohol telechelic and at least onepolyisocyanate. The aminoalcohol telechelic can be linear, branched,block, graft, monodisperse, polydisperse, regular, irregular, tactic,isotactic, syndiotactic, stereoregular, atactic, stereoblock,single-strand, double-strand, star, comb, dendritic, and/or ionomeric.The aminoalcohol telechelic can be chosen from homopolymers, randomcopolymers, pseudo-copolymers, statistical copolymers, alternatingcopolymers, periodic copolymer, bipolymers, terpolymers, andquaterpolymers. The aminoalcohol telechelic can comprise at least onepolymeric structure chosen from polyhydrocarbons, polyethers,polyesters, polyamides, polycarbonates, polyacrylates, polysiloxanes,and copolymers thereof. The composition can further comprise at leastone reactant chosen from isocyanates and curatives, or at least oneisocyanate-containing prepolymer where the aminoalcohol telechelic isused to cure the prepolymer. The aminoalcohol telechelic can be areaction product of at least one polyamine telechelic and at least onecyclic compound chosen from cyclic esters and cyclic amides. Thepolyamine telechelic can have a molecular weight of 200-5,000, and canbe a polyether polyamine chosen from diamines and triamines ofpolyoxyethylene, polyoxypropylene, andpoly(oxyethylene-co-oxypropylene). The cyclic compound can be chosenfrom caprolactone, caprolactone diols, and caprolactone triols. Thepoly(urethane-co-urea) prepolymer can be an in situ polymerizationproduct of at least one polyamine telechelic, at least one cyclic esterand/or cyclic amide, and at least one polyisocyanate chosen fromuretdione dimers and isocyanurate trimers. The poly(urethane-co-urea)prepolymer can have a viscosity of 1,000-4,000 cP at temperatures ofabout 125° C. or less.

The material can at least in part form at least one portion of the golfball chosen from inner center, core, inner core layer, intermediate corelayer, outer core layer, intermediate layer, cover, inner cover layer,intermediate cover layer, outer cover layer, discontinuous layer, woundlayer, foamed layer, lattice network layer, web or net, adhesion orcoupling layer, barrier layer, layer of uniformed or non-uniformedthickness, layer having a plurality of discrete elements, and layerfilled with liquid, gel, powder, and/or gas. In one example, the golfball can comprise a core comprising at least a first portion, and acover comprising at least a second portion, wherein the material isdisposed in at least one of the first and second portions, and/orbetween the core and the cover. The material can at least in part format least one cover layer having a thickness of 0.125 inches or less anda Shore D hardness of 20-80.

Golf equipment can be formed from a variety of compositions. Balata, anatural or synthetic trans-polyisoprene rubber, has been used to formgolf ball covers. Olefinic ionomer resins have also been used as covermaterials. Chemically, olefinic ionomer resins are copolymers of olefin(such as ethylene) and α,β-ethylenically unsaturated carboxylic acid(such as acrylic acid or methacrylic acid) that have 10% to 100% of thecarboxylic acid groups neutralized by cations (such as metal cations).Examples of commercially available olefinic ionomer resins include, butare not limited to, SURLYN® from Du Pont de Nemours and Company, andESCOR® and IOTEK® from ExxonMobil.

Polyurethanes are useful materials for golf ball covers. Polyurethanecovers can be polyurethane prepolymers cured with curing agents havingat least one active hydrogen groups (such as amines and/or polyols),wherein the prepolymers are formed of hydroxy-terminated telechelicswith polyisocyanates. Polyureas formed of polyurea prepolymers andcuratives are relatively new choices for golf ball materials.Polyurethanes and polyureas can be thermoset or thermoplastic, dependingat least in part on the curing agent used. Unsaturated components (suchas aromatic diisocyanate, aromatic polyol, and/or aromatic polyamine)used in a polyurethane or polyurea composition are at least in partresponsible for the composition's susceptibility to discoloration anddegradation upon exposure to thermal and actinic radiation, such asultraviolet (UV) light. Substituting the unsaturated components withpartially unsaturated or saturated components can enhance lightstability of the composition. Highly light-stable compositions mayinclude only substantially saturated components. As used herein, theterm “saturated” or “substantially saturated” means that the compound ormaterial of interest is fully saturated (i.e., contains no double bonds,triple bonds, or aromatic ring structures), or that the extent ofunsaturation is negligible, e.g., as shown by a bromine number inaccordance with ASTM E234-98 of less than 10, such as less than 5. Thecompositions of the disclosure may also include at least one lightstabilizer to improve light stability, especially when unsaturated(e.g., aromatic) components are used.

Moisture absorption is another mechanism through which desirablephysical properties in the composition are compromised. This can beremedied, for example, by incorporating at least one moisture vaporbarrier layer in the golf ball. Alternatively, the use ofwater/moisture-resistant compositions in golf ball components leads to agolf ball with improved shelf-life and/or use-life. Conventionalpolyurethane and polyurea golf ball covers can be prone to absorption ofmoisture. Incorporation of hydrophobic backbones into the compositionscan reduce moisture absorption and water/moisture permeability, asreflected in reduced water vapor transmission rate (WVTR).

As used herein, the terms “araliphatic,” “aryl aliphatic,” or “aromaticaliphatic” all refer to compounds that contain one or more aromaticmoieties and one or more aliphatic moieties, where the reactablefunctional groups such as, without limitation, isocyanate groups, aminegroups, and hydroxyl groups are directly linked to the aliphaticmoieties and not directly bonded to the aromatic moieties. Illustrativeexamples of araliphatic compounds are o-, m-, and p-tetramethylxylenediisocyanate (TMXDI).

The subscript letters such as m, n, x, y, and z used herein within thegeneric structures are understood by one of ordinary skill in the art asthe degree of polymerization (i.e., the number of consecutivelyrepeating units). In the case of molecularly uniformed products, thesenumbers are commonly integers, if not zero. In the case of molecularlynon-uniformed products, these numbers are averaged numbers not limitedto integers, if not zero, and are understood to be the average degree ofpolymerization.

Any numeric references to amounts, unless otherwise specified, are “byweight.” The term “equivalent weight” is a calculated value based on therelative amounts of the various ingredients used in making the specifiedmaterial and is based on the solids of the specified material. Therelative amounts are those that result in the theoretical weight ingrams of the material, like a polymer, produced from the ingredients andgive a theoretical number of the particular functional group that ispresent in the resulting polymer.

As used herein, the term “polymer” is used to refer to oligomers,adducts, homopolymers, random copolymers, pseudo-copolymers, statisticalcopolymers, alternating copolymers, periodic copolymer, bipolymers,terpolymers, quaterpolymers, other forms of copolymers, substitutedderivatives thereof, and mixtures thereof. These polymers can be linear,branched, block, graft, monodisperse, polydisperse, regular, irregular,tactic, isotactic, syndiotactic, stereoregular, atactic, stereoblock,single-strand, double-strand, star, comb, dendritic, and/or ionomeric.

As used herein, the term “telechelic” is used to refer to polymershaving at least two terminal reactive end-groups and capable of enteringinto further polymerization through these reactive end-groups. Reactiveend-groups disclosed herein include, without limitation, amine groups,hydroxyl groups, isocyanate groups, carboxylic acid groups, thiolgroups, and combinations thereof.

Other than in the operating examples, or unless otherwise expresslyspecified, all of the numerical ranges, amounts, values and percentagessuch as those for amounts of materials, times and temperatures ofreaction, ratios of amounts, values for molecular weight (whether numberaverage molecular weight (“M_(n)”) or weight average molecular weight(“M_(w)”), and others in the following portion of the specification maybe read as if prefaced by the word “about” even though the term “about”may not expressly appear with the value, amount or range. Accordingly,unless indicated to the contrary, the numerical parameters set forth inthe following specification and attached claims are approximations thatmay vary depending upon the desired properties sought to be obtained bythe present disclosure. At the very least, and not as an attempt tolimit the application of the doctrine of equivalents to the scope of theclaims, each numerical parameter should at least be construed in lightof the number of reported significant digits and by applying ordinaryrounding techniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the disclosure are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Furthermore, when numerical ranges ofvarying scope are set forth herein, it is contemplated that anycombination of these values inclusive of the recited values may be used.

For molecular weights, whether M_(n) or M_(w), these quantities aredetermined by gel permeation chromatography using polystyrene asstandards as is well known to those skilled in the art and such as isdiscussed in U.S. Pat. No. 4,739,019 at column 4, lines 2-45, which isincorporated herein by reference in its entirety.

As used herein, the terms “formed from” and “formed of” denote open,e.g., “comprising,” claim language. As such, it is intended that acomposition “formed from” or “formed of” a list of recited components bea composition comprising at least these recited components, and canfurther comprise other non-recited components during formulation of thecomposition.

As used herein, the term “cure” as used in connection with acomposition, e.g., “a curable material,” “a cured composition,” shallmean that any crosslinkable components of the composition are at leastpartially crosslinked. In certain examples of the present disclosure,the crosslink density of the crosslinkable components, i.e., the degreeof crosslinking, can range from 5% to 100% of complete crosslinking. Inother examples, the crosslink density can range from 35% to 85% of fullcrosslinking. In other examples, the crosslink density can range from50% to 85% of full crosslinking. One skilled in the art will understandthat the presence and degree of crosslinking, i.e., the crosslinkdensity, can be determined by a variety of methods, such as dynamicmechanical thermal analysis (DMTA) in accordance with ASTM E1640-99.

The compositions of the present disclosure typically comprise a reactionproduct of a polyisocyanate and one or more reactants. In one example,the reaction product can be a polyurethane formed from a polyurethaneprepolymer and a curative, the polyurethane prepolymer being a reactionproduct of a polyol telechelic and an isocyanate. The polyol telecheliccomprises at least two terminal hydroxyl end-groups that areindependently primary, secondary, or tertiary. The polyol telechelic canfurther comprise additional hydroxyl groups that are independentlylocated at the termini, attached directly to the backbone as pendantgroups, and/or located within pendant moieties attached to the backbone.The polyol telechelic can be α,ω-hydroxy telechelics havingisocyanate-reactive hydroxyl end-groups on opposing termini. All polyoltelechelics are polyols, which also include monomers, dimers, trimers,adducts, and the like having two or more hydroxyl groups.

In another example, the reaction product can be a polyurea formed from apolyurea prepolymer and a curative, the polyurea prepolymer being areaction product of a polyamine telechelic and an isocyanate. Thepolyamine telechelic comprises at least two terminal amine end-groupsthat are independently primary or secondary. The polyamine telecheliccan further comprise additional amine groups that are independentlyprimary or secondary, and are independently located at the termini,attached directly to the backbone as pendant groups, located within thebackbone, or located within pendant moieties that are attached to thebackbone. The secondary amine moieties may in part form single-ring ormulti-ring heterocyclic structures having one or more nitrogen atoms asmembers of the rings. The polyamine telechelic can be α,ω-aminotelechelics having isocyanate-reactive amine end groups on opposingtermini. All polyamine telechelics are polyamines, which also includemonomers, dimers, trimers, adducts, and the like having two or moreamine groups.

In a further example, the reaction product can be a poly(urethane-urea)formed from a poly(urethane-urea) prepolymer and a curative. Thepoly(urethane-urea) prepolymer can be a reaction product of anisocyanate and a blend of polyol and polyamine telechelics.Alternatively, the poly(urethane-urea) prepolymer can be a reactionproduct of an aminoalcohol telechelic and an isocyanate. Theaminoalcohol telechelic comprises at least one primary or secondaryterminal amine end-group and at least one terminal hydroxyl end-group.The polyamine telechelic can further comprise additional amine and/orhydroxyl groups that are independently located at the termini, attacheddirectly to the backbone as pendant groups, located within the backbone,or located within pendant moieties that are attached to the backbone.The secondary amine moieties may in part form single-ring or multi-ringheterocyclic structures having one or more nitrogen atoms as members ofthe rings. The aminoalcohol telechelic can be α-amino-ω-hydroxytelechelics having isocyanate-reactive amine and hydroxyl end groups onopposing termini. All aminoalcohol telechelics are aminoalcohols, whichalso include monomers, dimers, trimers, adducts, and the like having atleast one amine group and at least one hydroxyl group.

Any one or combination of two or more of the isocyanate-reactiveingredients disclosed herein can react with stoichiometrically deficientamounts of polyisocyanate such as diisocyanate to form elastomers thatare substantially free of hard segments. Such elastomers can have rubberelasticity and wear resistance and strength, and can be millable.

Polyamine Telechelics

Polyamine telechelics have two, three, four, or more amine end-groupscapable of forming urea linkages (such as with isocyanate groups), amidelinkages (such as with carboxyl group), imide linkages, and/or otherlinkages with other organic moieties. As such, polyamine telechelics canbe reacted with polyacids to form amide-containing polyamine or polyacidtelechelics, be reacted with isocyanates to form polyurea prepolymers,and be used as curatives to cure various prepolymers. Any one or more ofthe hydrogen atoms in the polyamine telechelic (other than those in theterminal amine end-groups) may be substituted with halogens, cationicgroups, anionic groups, silicon-based moieties, ester moieties, ethermoieties, amide moieties, urethane moieties, urea moieties,ethylenically unsaturated moieties, acetylenically unsaturated moieties,aromatic moieties, heterocyclic moieties, hydroxy groups, amine groups,cyano groups, nitro groups, and/or any other organic moieties. Forexample, the polyamine telechelics may be halogenated, such as havingfluorinated backbones and/or N-alkylated fluorinated side chains.

Any polyamine telechelics available or known to one of ordinary skill inthe art are suitable for use in compositions of the present disclosure.The M_(w) of the polyamine telechelics can be about 100-20,000, such asabout 150, about 200, about 230, about 500, about 600, about 1,000,about 1,500, about 2,000, about 2,500, about 3,000, about 3,500, about4,000, about 5,000, about 8,000, about 10,000, about 12,000, about15,000, or any M_(w) therebetween. The polyamine telechelic can compriseone or more hydrophobic and/or hydrophilic segments.

Exemplary polyamine telechelics, such as α,ω-amino telechelics, includepolyamine polyhydrocarbons (e.g., polyamine polyolefins), polyaminepolyethers, polyamine polyesters (e.g., polyamine polycaprolactones),polyamine polyamides (e.g., polyamine polycaprolactams), polyaminepolycarbonates, polyamine polyacrylates (e.g., polyaminepolyalkylacrylates), polyamine polysiloxanes, polyamine polyimines,polyamine polyimides, and polyamine copolymers including polyaminepolyolefinsiloxanes (such as α,ω-diaminopoly(butadiene-dimethylsiloxane) and α,ω-diaminopoly(isobutylene-dimethylsiloxane)), polyamine polyetherolefins (such asα,ω-diamino poly(butadiene-oxyethylene)), polyamine polyetheresters,polyamine polyethercarbonates, polyamine polyetheramides, polyaminepolyetheracrylates, polyamine polyethersiloxanes, polyaminepolyesterolefins (such as α,ω-diamino poly(butadiene-caprolactone) andα,ω-diamino poly(isobutylene-caprolactone)), polyamine polyesteramides,polyamine polyestercarbonates, polyamine polyesteracrylates, polyaminepolyestersiloxanes, polyamine polyamideolefins, polyaminepolyamidecarbonates, polyamine polyamideacrylates, polyaminepolyamidesiloxanes, polyamine polyamideimides, polyaminepolycarbonateolefins, polyamine polycarbonateacrylates, polyaminepolycarbonatesiloxanes, polyamine polyacrylateolefins (such asα,ω-diamino poly(butadiene-methyl methacrylate), α,ω-diaminopoly(isobutylene-t-butyl methacrylate), α,ω-diamino poly(methylmethacrylate-butadiene-methyl methacrylate)), polyaminepolyacrylatesiloxanes, polyamine polyetheresteramides, any otherpolyamine copolymers, as well as blends thereof.

a) Polyamine Polyhydrocarbons

An example of polyamine polyhydrocarbons has a generic structure of:

where R₁ and R₂ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R₃, R₄, and R₅ areindependently chosen from linear, branched, cyclic (includingmonocyclic, aromatic, bridged cyclic, spiro cyclic, fused polycyclic,and ring assemblies), saturated, unsaturated, hydrogenated, and/orsubstituted hydrocarbon moieties having 1 to about 30 carbon atoms; x,y, and z are independently zero to about 200, and x+y+z≧2. R₁ and R₂ canbe linear or branched structures having about 20 carbon atoms or less,such as 1-12 carbon atoms. R₃, R₄, and R₅ can independently have thestructure C_(n)H_(m), where n is an integer of about 2-20, and m is zeroto about 40. Any one or more of the hydrogen atoms in R₁ to R₅ may besubstituted with halogens, cationic groups, anionic groups,silicon-based moieties, ester groups, ether groups, amide groups,urethane groups, urea groups, ethylenically unsaturated groups,acetylenically unsaturated groups, hydroxy groups, amine groups, or anyother organic moieties. R₁ and R₂ can be identical. At least one of R₃,R₄, and R₅ can have the structure C_(n)H_(2n), n being an integer ofabout 2-12, and x+y+z is about 5-100.

The polyamine polyhydrocarbon can have one of the following structures:

where x is the chain length, i.e., 1 or greater; n is about 1-12; and Ris alkyl group having 1 to about 20, such as 1-12, carbon atoms, aphenyl group, a cyclic group, or mixture thereof.

Polyamine polyhydrocarbons are hydrophobic in general, and can providereduced moisture absorption and permeability to the resultingcompositions. Non-limiting examples of polyamine polyhydrocarbonsinclude α,ω-diamino polyolefins such as α,ω-diamino polyethylenes,α,ω-diamino polypropylenes, α,ω-diamino polyethylenepropylenes,α,ω-diamino polyisobutylenes, α,ω-diamino polyethylenebutylenes (withbutylene content of at least about 25% by weight, such as at least 50%),amine-terminated Kraton rubbers; α,ω-diamino polydienes such α,ω-diaminopolyisoprenes, partially or fully hydrogenated α,ω-diaminopolyisoprenes, amine-terminated liquid isoprene rubbers, α,ω-diaminopolybutadienes, partially and/or fully hydrogenated α,ω-diaminopolybutadienes; as well α,ω-diamino poly(olefin-diene)s such asα,ω-diamino poly(styrene-butadiene)s, α,ω-diaminopoly(ethylene-butadiene)s, and α,ω-diaminopoly(butadiene-styrene-butadiene)s.

One group of polyamine polyhydrocarbons is polyamine polyalkyleneshaving a plurality of secondary or tertiary amine moieties, such asthose having the formula R′HN—(R—N(R′))_(n)—H, where R is the same ordifferent alkyl, aryl, aralkyl, alicyclic, cycloalkyl, and alkoxygroups; R′ is the same or different moieties chosen from hydrogen,alkyl, aryl, aralkyl, alicyclic, cycloalkyl, and alkoxy groups; n isabout 5 or greater, such as about 10 or greater. R and R′ canindependently have 1 to about 20 carbon atoms, such as 1-12 carbonatoms, or about 1-4 carbon atoms.

Another group of polyamine polyhydrocarbons is polyamine polydienes,which also include polyamine poly(alkylene-diene)s, as well as blendsthereof. Suitable polyamine polydienes have M_(n) of about 1,000-20,000,such as about 1,000-10,000, or about 3,000-6,000, and an aminefunctionality of about 1.6-10, such as about 1.8-6, or about 1.8-2. Thediene monomers can be conjugated dienes such as 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, and mixtures thereof. The polyaminepolydiene can be substantially hydrogenated to improve stability, suchthat at least about 90%, or at least about 95%, of the carbon-carbondouble bonds in the polydiene are hydrogenated.

The elastomer compositions of the present disclosure can be resilient.Resilience can be measured, for example, by determining the percentageof the original height to which a ½″ steel ball will rebound after beingdropped onto an immobilized ½″ thick elastomer sample from a height ofone meter. A resilient elastomer can display a rebound height percentageof greater than 60%, such as greater than about 70%, or greater thanabout 75%.

Diamino polydienes and diamino copolydienes, among other polyaminetelechelics, are capable of imparting high resiliency in thecompositions. The diamino polydiene can be diamino polybutadiene having1,4-addition of about 30-70%, such as about 40-60%. The diaminopolybutadiene can have 1,2-addition of at least about 40%, such as about40-60%. The hydrogenated diamino polybutadiene can remain liquid atambient temperature. In one example, the diamino polybutadiene can bemore than about 99% hydrogenated, having M_(n) of about 3,300, an aminefunctionality of about 1.92, and a 1,2-addition content of about 54%. Inanother example, the diamino polydiene can be diamino polyisoprenehaving 1,4-addition of at least about 80% and moderate glass transitiontemperature and viscosity.

One group of diamino copolydienes has a generic structure of:

where R₁ and R₂ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R₃ is hydrogen,linear or branched alkyl group (such as methyl or t-butyl), cyano group,phenyl group, halide, or a mixture thereof; R₄ is hydrogen, linear orbranched alkyl group, halide (such as chloride or fluoride), or amixture thereof; x and y are independently about 1-200. R₁ and R₂ can belinear or branched, having about 20 carbon atoms or less, such as 1-12carbon atoms. The y:x ratio can be about 82:18 to about 90:10. Thediamino copolydiene can be substantially hydrogenated (i.e.,substantially all of the >C══CH— or >C══CH₂ moieties are hydrogenatedinto >CH—CH₂— or >C—CH₃ moieties, respectively). One example can behydrogenated diamino poly(acrylonitrile-co-butadiene) where R₃ is cyanogroup and R₄ is hydrogen.

Polyamine polyhydrocarbons can also be derived from polyolpolyhydrocarbons through means such as amination, or reaction withaminoalcohols, amino acids, or cyclic amides. For example, polyolpolyhydrocarbons can be end-capped with 2-, 3-, and/or 4-aminobenzoicacid and the likes thereof as disclosed herein to form aminobenzoatederivatives, e.g., polymethylene-di-p-aminobenzoates.

b) Polyamine Polyethers

An example of the polyamine polyethers has a generic structure of:

where R₁ and R₂ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R₃ to R₆ areindependently linear, branched, or cyclic moieties having at least onecarbon atom, such as about 2-60 carbon atoms; i is about 2-10, such asabout 2-6; x is about 1-200, and y and z are independently zero to about200. R₁ and R₂ can be linear or branched structures having about 20carbon atoms or less, such as 1-12 carbon atoms. Any one or more of thehydrogen atoms in R₁ to R₆ may be substituted with halogens, cationicgroups, anionic groups, silicon-based moieties, ester groups, ethergroups, amide groups, urethane groups, urea groups, ethylenicallyunsaturated groups, acetylenically unsaturated groups, hydroxy groups,amine groups, or any other organic moieties. R₁ and R₂ can be identical.R₃ to R₆ can independently have the structure C_(n)H_(m), where n is aninteger of about 1-30, and m is an integer of about 2-60. R₃ and R₅ canbe identical. The number x can be about 2-70, such as about 5-50, orabout 12-35. Alternatively, y+z can be about 2-10, while x can be about8-50.

Commercial examples of polyamine polyethers include, but are not limitedto, polyoxyethylene diamines, polyoxypropylene diamines (such asJeffamine® D2000 from Huntsman Corporation, Austin, Tex.),α,ω-bis(2-aminopropyl)polyoxypropylenes (such as those having M_(w)about 200-5,000), polyoxytetramethylene diamines, modifiedpolyoxytetramethylene diamines, poly(oxyethylene-oxypropylene) diamines,α,ω-bis(3-aminopropyl)polytetrahydrofurans (such as those having M_(w)about 200-2,000), poly(oxyethylene-capped oxypropylene) diamines,poly(oxybutylene-oxypropylene-oxyethylene) diamines, polyoxyalkylenediamines initiated by bisphenol A or primary monoamines, tri-blockpolyether polyamines such aspoly(oxypropylene-block-oxyethylene-block-oxypropylene) diamines andpoly(oxyethylene-block-oxypropylene-block-oxyethylene) diamines,polyoxypropylene triamines initiated by glycerin, trimethylolethane, ortrimethylolpropane, polyoxypropylene tetramines initiated bypentaerythritol, ethylene diamine, phenolic resin, or methyl glucoside,diethylenetriamine-initiated polyoxypropylene pentamines,sorbitol-initiated polyoxypropylene hexamines, and sucrose-initiatedpolyoxypropylene octamines. Other suitable polyether polyamines includethose disclosed in co-pending application Ser. No. 10/434,739.

In one example, the polyamine polyether has the structure of (3), whereR₃ and R₅ are the same linear, branched, or cyclic radicals having atleast about 10 carbon atoms, such as at least about 18 carbon atoms, orat least about 30 carbon atoms, and y and z are zero, so that thegeneric structure becomes R₁HN—[R₃—O]_(x)—R₃—NHR₂, where R₁ to R₃ are asdescribed above. In one example, R₃ is an alkylene moiety, while x isabout 1-50, such as about 1.5-30. These polyamine polyethers can behighly hydrophobic. When x is about 10 or less, such as 1.5, 2, 4, 5, 7,or any number therebetween, these polyamine polyethers are typicallyliquid at ambient temperature, having a viscosity at 25° C. of about3,000-12,000 cP. The hydrophobicity of such polyamine polyethers canenhance hydrolysis resistance of the compositions and reduce moistureabsorption.

In another example, the polyamine polyether has the structure of (3),where R₅ and R₆ are identical, R₄ and R₅ are the same or differentalkylene groups having about 2-40 carbon atoms, such as about 2-20carbon atoms, or about 2-10 carbon atoms, or about 2-4 carbon atoms, R₃is a backbone of a dimer diol, fatty polyol, or oleochemical polyols asdisclosed herein below, x is 1, and 40≧(y+z)≧1. As such, the structure(3) becomes R₁HN—[R₄—O]_(y)—R₃—[O—R₅]_(z+1)—NHR₂, where R₁ to R₅ are asdescribed above. These polyamine polyethers are hydrolysis-resistant,and typically have M_(n) of about 600-3,000.

To enhance resilience of the compositions of the present disclosure, thehydroxy-terminated and/or amine-terminated polymers as described hereincan have oxyethylene moieties at the terminals, such as in directattachment with the amine and/or hydroxyl end-groups, and the content ofthe terminal oxyethylene moieties can be about 5-30% by weight of thepolymer. The oxyethylene moieties can be added to hydroxy-terminatedand/or carboxyl-terminated polymers via ring-opening polymerization ofethylene oxide with an alkali catalyst such as alkali metal, alkalimetal hydroxide, alkali metal alkoxide, and double metal cyanidecomplex.

For resilient elastomer compositions, a blend of two polyaminepolyethers can be used to react with isocyanate and form the prepolymer,wherein the first polyamine polyether has a first molecular weight ofabout 3,500-6,500, a first amine functionality of about 3 or less, and afirst oxyethylene content of about 8-20% by weight, while the secondpolyamine polyether has a second molecular weight of about 4,000-7,000,a second amine functionality of about 4-8, and a second oxyethylenecontent of about 5-15% by weight. The first polyamine polyether mayconstitute about 70-98% by weight of the blend, while the secondpolyamine polyether may constitute about 2-30% by weight of the blend.Alternatively, a mixture having about 25-95% of the polyamine polyetherblend and about 5-75% of at least a third polyamine telechelic differentfrom the first and second polyamine polyethers is also suitable toformulate a resilient elastomer composition.

In another resilient composition, the polyamine telechelic is apolyether triamine having M_(n) of about 4,500-6,000 and an averageamine functionality of about 2.4-3.5, such as about 2.4-2.7. In afurther resilient example, the polyamine polyether may have a weightaverage unsaturation of about 0.03 meq/g or less (measured by ASTMD-2849-69), such as about 0.02 meq/g or less, or about 0.015 meq/g orless, or about 0.01 meq/g or less, and M_(n) of about 1,500-5,000. Thepolyamine polyether may comprise at least one randompoly(oxyethylene-oxyalkylene) terminal block or polyoxyethylene terminalblock, with an oxyethylene content of about 12-30% by weight. Lowunsaturation in the polyamine polyethers of about 0.002-0.007 meq/g isachieved by using double metal cyanide catalysts when forming thepolyether backbone. Concomitant to the low unsaturation, the polyaminepolyethers may also have a low polydispersity of about 1.2 or less.

In a further example, the polyamine polyether can have repeatingbranched oxyalkylene monomer units derived from branched diol monomers,chiral diol monomers, alkylated cyclic ethers, and/or chiral cyclicethers, through homo-polymerization, co-polymerization, and/orring-opening polymerization. The polyamine polyethers can be obtained byaminating polyol polyethers formed from chiral diol/ether and achiraldiol/ether at a molar ratio of about 85:15 to about 20:80. Anon-limiting example of such polyol polyethers is referred to as amodified polytetramethylene ether glycol (“PTMEG”) diamine, or anamine-terminated poly(tetrahydrofuran-co-methyltetrahydrofuran) ether.

Other generic structures for polyamine polyethers include:

where x is the chain length, i.e., 1 or greater, n is about 1-12, and Ris any C₁ to C₂₀ or C₁ to C₁₂ alkyl group, phenyl group, cyclic group,or mixture thereof;

wherein x is about 1-70, such as about 5-50 or about 12-35, R is any C₁to C₂₀ or C₁ to C₁₂ alkyl group, phenyl group, cyclic group, or mixturethereof, and R₃ is hydrogen, methyl group, or mixture thereof;

wherein x+z is about 3.6-8, y is about 9-50, R is any C₁ to C₂₀ or C₁ toC₁₂ alkyl group, phenyl group, cyclic group, or mixture thereof, R₁ is—(CH₂)_(a)— with a being about 1-10, phenylene moiety, cyclic moiety, ormixture thereof, and R₃ is hydrogen, methyl group, or mixture thereof;H₂N—R₁—O—R₁—O—R₁—NH₂, H₂N—R₁—O—R₁—O—R₁—NHR, or RHN—R₁—O—R₁—O—R₁—NHRwherein R is any C₁ to C₂₀ or C₁ to C₁₂ alkyl group, phenyl group,cyclic group, or mixture thereof, and R₁ is —(CH₂)_(a)— with a beingabout 1-10, phenylene moiety, cyclic moiety, or mixture thereof;

where x and n are chain lengths, i.e., 1 or greater, n is about 1-12,such as about 2, R and R₁ are independently chosen from linear orbranched alkyl groups having about 1-20 carbon atoms, such as about 1-12carbon atoms, phenyl group, cyclic group, or mixtures thereof, and R₂ ishydrogen, methyl group, or mixture thereof;

where m is 1 or greater, such as about 1-6, or about 2, m is 1 orgreater, such as about 1-12, or about 2, R is any C₁ to C₂₀ or C₁ to C₁₂alkyl group, phenyl group, cyclic group, or mixture thereof, and R₁ andR₂ are independently chosen from hydrogen, methyl group, or mixturethereof.

c) Polyamine Polyesters

An example of the polyamine polyesters has a generic structure of:

where R₁ and R₂ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R₃ to R₉ areindependently linear, branched, or cyclic moieties having at least onecarbon atom, such as about 2-60 carbon atoms; Z is the same or differentmoieties chosen from —O— and —NH—; i is about 2-10, such as about 2-6; xis the same or different numbers of about 1-200, and y and z areindependently zero to about 200. R₁ and R₂ can be linear or branchedstructures having about 20 carbon atoms or less, such as 1-12 carbonatoms. R₃ to R₉ can independently have the structure C_(n)H_(m), where nis an integer of about 2-30, and m is an integer of about 2-60. Thenumber y can be 1 or greater, and less than the number x. Any one ormore of the hydrogen atoms in R₁ to R₉ may be substituted with halogens,cationic groups, anionic groups, silicon-based moieties, ester groups,ether groups, amide groups, urethane groups, urea groups, ethylenicallyunsaturated groups, acetylenically unsaturated groups, hydroxy groups,amine groups, or any other organic moieties. R₁ and R₂ can be identical.R₄ and R₅ can be identical. R₃ and R₆ can be identical, having astructure of C_(n)H_(2n), n being an integer of about 2-30, x+y+z isabout 1-100, such as about 5-50. The number y can be 1 or greater andless than the number x.

Examples of polyamine polyesters include, without limitation,poly(ethylene adipate) diamines, poly(butylene adipate) diamines,poly(1,4-butylene glutarate) diamines, poly(ethylene propylene adipate)diamines, poly(ethylene butylene adipate) diamines, poly(hexamethyleneadipate) diamines, poly(hexamethylene butylene adipate) diamines,poly(hexamethylene phthalate) diamines, poly(hexamethyleneterephthalate) diamines, poly(2-methyl-1,3-propylene adipate) diamines,poly(2-methyl-1,3-propylene glutarate) diamines, andpoly(2-ethyl-1,3-hexylene sebacate) diamines. Non-limiting examples ofpolyester polyamines based on fatty polyacids or polyacid adducts, suchas those disclosed herein, include poly(dimer acid-co-ethylene glycol)hydrogenated diamines and poly(dimer acid-co-1,6-hexanediol-co-adipicacid) hydrogenated diamines.

Other generic structures of polyamine polyesters include:

where x is the chain length, i.e., 1 or greater, such as about 1-20, Ris any C₁ to C₂₀ or C₁ to C₁₂ alkyl group, phenyl group, cyclic group,or mixture thereof, and R₁ and R₂ are independently chosen from straightor branched hydrocarbon chains, e.g., alkylene or arylene chains.

The polyamine polyester can have a crystallization enthalpy of at mostabout 70 J/g and M_(n) of about 1,000-7,000, such as about 1,000-5,000.This polyamine polyester can be blended with a polyamine polyetherhaving M_(n) of about 500-2,500. The average amine functionality of theblend, which is the ratio of total number of amine groups in the blendto total number of telechelic molecules in the blend, can be about2-2.1. The polyamine polyester can have an ester content (number ofester bonds/number of all carbon atoms) of about 0.2 or less, such asabout 0.08-0.17.

An example of the polyamine polycaprolactones has a generic structureof:

where R₁ to R₄, Z, i, x are as described above. In one example, x isabout 5-100, and y is 1 or greater and less than the number x. Suitablepolyamine polycaprolactones include, but are not limited to, aminationderivatives of polyol polycaprolactones disclosed herein, such as thoseproducts of polyamine-initiated and/or polyol-initiated ring-openingpolymerization of caprolactone, and polymerization products of hydroxycaproic acid. Suitable polyamine and polyol initiators include anypolyamines and polyols available to one of ordinary skill in the art,such as those disclosed herein, as well as any and all of the polyamineand polyol telechelics of the present disclosure. The caprolactonemonomer can be replaced by or blended with any other cyclic estersand/or cyclic amides disclosed herein to produce copolymer telechelics.

d) Polyamine Polyamides

An example of the polyamine polyamides has a generic structure of:

where R₁ and R₂ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R₃ to R₉ areindependently linear, branched, or cyclic moieties having at least onecarbon atom, such as about 2-60 carbon atoms; Z is the same or differentmoieties chosen from —O— and —NH—; i is about 2-10, such as about 2-6; xis the same or different numbers of about 1-200, and y and z areindependently zero to about 200. R₁ and R₂ can be linear or branchedstructures having about 20 carbon atoms or less, such as 1-12 carbonatoms. R₃ to R₉ can independently have the structure C_(n)H_(m), where nis an integer of about 2-30, and m is an integer of about 2-60. Any oneor more of the hydrogen atoms in R₁ to R₉ may be substituted withhalogens, cationic groups, anionic groups, silicon-based moieties, estergroups, ether groups, amide groups, urethane groups, urea groups,ethylenically unsaturated groups, acetylenically unsaturated groups,hydroxy groups, amine groups, or any other organic moieties. R₁ and R₂can be identical. R₃ and R₆ can be identical, having a structure ofC_(n)H_(2m), n being an integer of about 2-30, x+y+z can be about 1-100,such as about 5-50.

The polyamide chain above can be formed from condensation polymerizationreaction of polyacid (including polyacid telechelic) and polyamine(including polyamine telechelic), with an equivalent ratio of polyamineto polyacid being greater than 1, such as about 1.1-5 or about 2.Mixtures of polyacid and polyamine can be, for example, hexamethylenediammonium adipate, hexamethylenediammonium terephthalate, ortetramethylene diammonium adipate. Alternatively, the polyamide chaincan be formed partially or essentially from ring-opening polymerizationof cyclic amides such as caprolactam. The polyamide chain can also beformed partially or essentially from polymerization of amino acid,including those that structurally correspond to the cyclic amides.Obviously, the polyamide chain can comprise multiple segments formedfrom the same or different polyacids, polyamines, cyclic amides, and/oramino acids, non-limiting examples of which are disclosed herein.Suitable starting materials also include polyacid polymers, polyaminetelechelics, and amino acid polymers. At least one polyacid, polyamine,cyclic amide, or amino acid having M_(w) of at least about 200, such asat least about 400, or at least about 1,000 can be used to form thebackbone. A blend of at least two polyacids and/or a blend of at leasttwo polyamines can be used, wherein one has a molecular weight greaterthan the other. The polyacid or polyamine of smaller molecular weightcan contribute to hard segments in the polyamine polyamide, which mayimprove shear resistance of the resulting elastomer. For example, thefirst polyacid/polyamine can have a molecular weight of less than 2,000,and the second polyacid/polyamine can have a molecular weight of 2,000or greater. In one example, a polyamine blend can comprise a firstpolyamine having a M_(w) of 1,000 or less, such as Jeffamine® 400 (M_(w)about 400), and a second polyamine having a M_(w) of 1,500 or more, suchas Jeffamine® 2000 (M_(w) about 2,000). The backbone of the polyaminepolyamide can have about 1-100 amide linkages, such as about 2-50, orabout 2-20. Polyamine polyamides can be linear, branched, star-shaped,hyper-branched or dendritic (such as amine-terminated hyper-branchedquinoxaline-amide polymers of U.S. Pat. No. 6,642,347, the disclosure ofwhich is incorporated herein by reference).

An example of the polyamine polycaprolactams has a generic structure of:

where R₁ to R₃, Z, i, x are as described above. The number x can beabout 5-100. Polyamine polycaprolactams include, but are not limited to,those products of polyamine-initiated and/or polyol-initiatedring-opening polymerization of caprolactam, and polymerization productsof amino caproic acid. Suitable polyamine and polyol initiators includeany polyamines and polyols available to one of ordinary skill in theart, such as those disclosed herein, as well as any and all of thepolyamine and polyol telechelics of the present disclosure. Thecaprolactam monomer can be replaced by or blended with any other cyclicesters and/or cyclic amides disclosed herein to produce copolymertelechelics.

Non-limiting examples of polyamine-initiated polycaprolactam polyaminesinclude bis(2-aminoethyl)ether-initiated polycaprolactam polyamines,polyoxyethylenediamine-initiated polycaprolactam polyamines,propylenediamine-initiated polycaprolactam polyamines,polyoxypropylenediamine-initiated polycaprolactam polyamines,1,4-butanediamine-initiated polycaprolactam polyamines,trimethylolpropane-based triamine-initiated polycaprolactam polyamines,neopentyldiamine-initiated polycaprolactam polyamines,hexanediamine-initiated polycaprolactam polyamines,polytetrahydrofurandiamine-initiated polycaprolactam polyamines, andmixtures thereof. Non-limiting examples of polyol-initiatedpolycaprolactams are bis(2-hydroxyethyl) ether initiated polycaprolactampolyamines, 2-(2-aminoethylamino) ethanol initiated polycaprolactampolyamines, polyoxyethylene diol initiated polycaprolactam polyamines,propylene diol initiated polycaprolactam polyamines, polyoxypropylenediol initiated polycaprolactam polyamines, 1,4-butanediol initiatedpolycaprolactam polyamines, trimethylolpropane-initiated polycaprolactampolyamines, hexanediol-initiated polycaprolactam polyamines,polytetramethylene ether diol initiated polycaprolactam polyamines, andmixtures thereof.

Non-limiting examples of polyacid telechelics include polyacidpolycaprolactones and polyacid polycaprolactams having genericstructures of:

where R₃ is a linear, branched, or cyclic moiety having at least onecarbon atom, such as about 2-60 carbon atoms; Z is the same or differentmoieties chosen from —O— and —NH—; R is the same or different moietieschosen from linear or branched aliphatic, alicyclic, araliphatic, andaromatic moieties having 1-60 carbon atoms; i is about 2-10, such asabout 2-6; x is the same or different numbers of about 1-200, such as5-100; and y is the same or different numbers of 0 or 1.

e) Polyamine Polycarbonates

An example of the polyamine polycarbonates has a generic structure of:

where R₁ and R₂ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R₃ to R₆ areindependently chosen from linear, branched, cyclic, aliphatic,alicyclic, araliphatic, aromatic, and ether moieties having at least onecarbon atom, such as about 2-60 carbon atoms; x is about 1-200, and yand z are independently zero to about 200. R₁ and R₂ can be linear orbranched structures having about 20 carbon atoms or less, such as 1-12carbon atoms. R₃ to R₆ can independently have the structure C_(n)H_(m),where n is an integer of about 2-30, and m is an integer of about 2-60.Any one or more of the hydrogen atoms in R₁ to R₆ may be substitutedwith halogens, cationic groups, anionic groups, silicon-based moieties,ester groups, ether groups, amide groups, urethane groups, urea groups,ethylenically unsaturated groups, acetylenically unsaturated groups,hydroxy groups, amine groups, or any other organic moieties. R₁ and R₂can be identical. R₃ and R₆ can be identical. R₃, R₅ and R₆ can all beidentical. The polyamine polycarbonate can be substantially free ofether linkages.

When y and z are both zero, the polyamine polycarbonate can besubstantially crystalline. Examples include poly(phthalate carbonate)diamines, poly(hexamethylene carbonate) diamines, and polycarbonatediamines comprising Bisphenol A. When at least one of y and z is greaterthan zero and R₃, R₄ and R₅ are different from each other, the polyaminepolycarbonate becomes amorphous due to reduction in cohesive energydensity, and displays lowered crystallinity, lowered hysteresis, andimproved impact resistance as compared to crystalline polyaminepolycarbonates. Non-limiting examples of R₃ to R₆ include —(CH₂)— wheren is about 1-16, such as hexamethylene (n=6); —CH₂C₆H₁₀CH₂—(1,4-cyclohexane dimethylene); —C₆H₅C(CH₃)₂C₆H₅-(bisphenol A); and—(C_(m)H_(2m)O)_(n)C_(m)H_(2m)— where m is about 1-6, and n is about1-16, such as trioxyethylene (m is 2, n is 2). A non-limiting example ofsuch amorphous polyamine copolycarbonate is α,ω-diaminopoly(hexamethylene carbonate-block-trioxyethylenecarbonate-block-hexamethylene carbonate). Polyamine polycarbonates maybe derived from polyol polycarbonates as disclosed herein, for example,through amination. In one example, the polyamine polycarbonate can haveat least one segment based exclusively or predominantly on1,6-hexanediol, in combination with diaryl carbonate, dialkyl carbonate,dioxolanone, phosgene, bis-chlorocarbonate, and/or urea.

Other polyamine polycarbonates can have the following structure:

where R₁ and R₂ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R₃ is chosen fromlinear, branched, cyclic, aliphatic, alicyclic, araliphatic, andaromatic moieties having about 4-40 carbon atoms, and alkoxy moietieshaving about 2-20 carbon atoms; R₄ is chosen from linear, branched,cyclic, aliphatic, alicyclic, araliphatic, and aromatic moieties havingabout 2-20 carbon atoms, and organic moieties having about 2-4 linearcarbon atoms in the main chain with or without one or more pendantcarbon groups; x is the same or different numbers of about 2-50, such asabout 2-35; and y is the same or different numbers chosen from 0, 1, and2.

Further polyamine polycarbonates can have one of the followingstructures:

where x is the chain length, such as about 1-20, R₁ is a straight chainhydrocarbon or predominantly bisphenol A units or derivatives thereof,R₂ is an alkylene moiety having about 1-20 or about 1-12 carbon atoms,phenylene moiety, cyclic moiety, or mixture thereof, and R is any C₁ toC₂₀ or C₁ to C₁₂ alkyl group, phenyl group, cyclic group, or mixturethereof.

f) Polyamine Polyimines

Linear and branched polyamine polyalkyleneimines may have respectivegeneric structures of:

where R is the same or different linear or branched divalent moieties,such as C₁ to C₆ alkylene moieties such as methylene, ethylene,propylene, butylene, amylene, or hexylene; R₁ is chosen from hydrogen,alkyl, aryl, aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R₂ andR₃ are the same or different moieties chosen from hydrogen, linear orbranched C₁ to C₈ alkyl groups, linear or branched C₁ to C₈ hydroxyalkyl groups, aryl groups, and hydroxy aryl groups; x, y, and z areindependently about 1-200. R₁ can be linear or branched structureshaving about 20 carbon atoms or less, such as 1-12 carbon atoms.Polyamine polyalkyleneimines can have a greater content of secondaryamines (such as about 50% or more) than primary and/or tertiary amines.Linear polyalkyleneimine chains can be prepared by hydrolyzing thecorresponding polyalkylene oxazolines (e.g., polyethyleneoxazolines).Branched polyalkyleneimines can be obtained by (co)polymerizing cyclicmonomers (e.g., ethylene imine). Non-limiting examples includepolyethyleneimines and polypropyleneimines. M_(w) of polyaminepolyalkyleneimines can be as low as about 500 and as high as about30,000. Polyamine polyimines may further contain grafted polymericsegments such as, without limitation, polyethylene glycol andmethoxylated polyethylene glycol. Linear, branched, and graftedpolyamine polyimines can be used alone or in combination of two or morethereof.

Linear or branched polyamine polyethyleneimines can have one of thefollowing structures:

wherein x and y are chain lengths, i.e., greater than 1, R is the sameor different moieties chosen from hydrogen, linear or branched alkylgroup having 1 to about 20 carbon atoms, such as 1-12 carbon atoms,phenyl group, cyclic group, or mixture thereof, and R₁ is chosen fromhydrogen, methyl group, or mixture thereof.

Other polyamine polyimines include polypropylenimine tetraminedendrimer, polypropylenimine octamine dendrimer, polypropyleniminehexadecamine dendrimer, polypropylenimine dotriacontamine dendrimer,polypropylenimine tetrahexacontamine dendrimer. These and otherhyper-branched and dendritic macromolecules are usable in thecompositions of the present disclosure, including dendrimers andtecto-dendrimers (having a core dendrimer surrounded by multipledendrimers of the same or different structure/surface functionality),and those described in co-owned and co-pending U.S. ApplicationPublication No. 2003/0236137, which are incorporated herein byreference. PAMAM dendrimers can have a variety of cores such asethylenediamine, cystamine, 1,4-diaminobutane, 1,6-diaminohexane, and1,12-diaminododecane, different generations from 0 to about 10, such asabout 2-6, and a variety of surface end-groups such as amine, hydroxyl,amidoethanol, amidoethylethanolamine, succinamic acid, sodiumcarboxylate, tris(hydroxymethyl)aminomethane, and combinations thereof.Such dendrimers are available from Dendritic Nanotechnologies of Mt.Pleasant, Mich. and Dendritech of Midland, Mich.

g) Polyamine Polyacrylates

An example of polyamine polyacrylates has a generic structure of:

where R₁ and R₂ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R₃ to R₈ areindependently chosen from hydrogen, aliphatic, alicyclic, aromatic,carbocyclic, heterocyclic, halogenated, and substituted moieties, eachhaving less than about 20 carbon atoms; X and Y are optional,independently being linear or branched alkyl, aryl, mercaptoalkyl,ether, ester, carbonate, acrylate, halogenated, or substituted moieties;x is about 1-200, and y and z are independently zero to about 100. R₁and R₂ can be linear or branched structures having about 20 carbon atomsor less, such as 1-12 carbon atoms. R₃ to R₈ can independently be linearor branched moieties having about 20 carbon atoms or less, such as ofthe structure C_(n)H_(m), where n is an integer of about 2-20, and m isan integer of about 2-40. Any one or more of the hydrogen atoms in R₁ toR₈ may be substituted with halogens, cationic groups, anionic groups,silicon-based moieties, ester groups, ether groups, amide groups,urethane groups, urea groups, ethylenically unsaturated groups,acetylenically unsaturated groups, hydroxy groups, amine groups, or anyother organic moieties. R₁ and R₂ can be identical. R₄, R₆, and R₈ canindependently be hydrogen or methyl group, while R₃, R₅, and R₇ canindependently have the structure of C_(n)H_(2n), n being an integer ofabout 2-16, x+y+z is about 1-100, such as about 5-50. Non-limitingexamples of polyalkylacrylate polyamines include α,ω-diaminopolymethylmethacrylates, α,ω-diamino polybutylmethacrylates, andα,ω-diamino polyethylhexylmethacrylates.

h) Polyamine Polysiloxanes

An example of polyamine polysiloxanes has a generic structure of:

where R₁ and R₂ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R₃ to R₈ areindependently chosen from hydrogen, aliphatic, alicyclic, aromatic,carbocyclic, heterocyclic, halogenated, and substituted moieties, suchas C₁ to C₈ linear, branched or cyclic alkyl or phenyl moieties; X and Yare optional, independently being linear or branched alkyl, aryl,mercaptoalkyl, ether, ester, carbonate, acrylate, halogenated, orsubstituted moieties; m is about 1-200; n is zero to about 100; z isabout 1-100. R₁ and R₂ can be linear or branched structures having about20 carbon atoms or less, such as 1-12 carbon atoms. R₃ to R₈ canindependently have linear or branched structure of C_(n)H_(m), where nis an integer of about 2-20, and m is an integer of about 2-40. Any oneor more of the hydrogen atoms in R₁ to R₈ may be substituted withhalogens, cationic groups, anionic groups, silicon-based moieties, estergroups, ether groups, amide groups, urethane groups, urea groups,ethylenically unsaturated groups, acetylenically unsaturated groups,hydroxy groups, amine groups, etc. R₁ and R₂ can be identical. In oneexample, R₃═R₄, R₅═R₆, and R₇═R₈.

Non-limiting examples of polyamine polysiloxanes include bis(aminoalkyl)polydimethylsiloxanes (such as bis(3-aminopropyl)polydimethylsiloxanes),poly(dimethylsiloxane-co-diphenylsiloxane) diamines,poly(dimethylsiloxane-co-methylhydrosiloxane) diamines, andpolydimethylsiloxane diamines. Non-limiting examples of polyaminecopolymers include polysiloxaneether polyamines obtained by aminatingthe reaction product of polysiloxane diol and polyether diol and/orcyclic ether, such as poly(dimethylsiloxane-oxyethylene) diamines, andpolysiloxaneester polyamines or polysiloxaneamide polyamines obtained byreacting polysiloxane diol with amino acid or cyclic amide,respectively.

i) Fatty Polyamine Telechelics

Fatty polyamine telechelics include hydrocarbon polyamine telechelics,adduct polyamine telechelics, and various oleochemical polyaminetelechelics. Hydrocarbon polyamine telechelics can have an all-carbonbackbone of about 8-100 carbon atoms, such as about 10, about 12, about18, about 20, about 25, about 30, about 36, about 44, about 54, about60, and any numbers therebetween. Fatty polyamine telechelics can bederived from corresponding fatty polyacids, such as by reacting thefatty polyacids with ammonia to obtain the corresponding nitriles whichmay then be hydrogenated to form the fatty polyamine telechelics.Alternatively, fatty polyamine telechelics can also be derived fromcorresponding fatty polyol telechelics through, for example, amination,reaction with suitable amino acids or esters thereof, reaction withsuitable cyclic amides, or reaction with suitable polyamines oraminoalcohols. These fatty polyamine telechelics can be liquid.

One form of adduct polyamine telechelics can be dimer diamines, whichcan be aliphatic α,ω-diamines having relatively high molecular weight.Dimer diamines can have a dimer content of greater than about 90%, suchas greater than about 95% by weight. The dimer diamines may beunsaturated, partly hydrogenated, or completely hydrogenated (i.e.,fully saturated). Non-limiting dimer diamines can have one of thefollowing structures:

where R is the same or different moieties chosen from hydrogen, alkyl,aryl, aralkyl, alicyclic, cycloalkyl, and alkoxy groups; x+y and m+n areboth at least about 8, such as at least about 10, such as 12, 14, 15,16, 18, 19, or greater.

Molecular weight of fatty polyamine telechelics can be about 200-15,000,such as about 250-12,000, or about 500-5,000. Fatty polyaminetelechelics can be liquid at room temperature, having low to moderateviscosity at 25° C. (e.g., about 100-5,000 cP or about 500-3,000 cP).Fatty polyamine telechelics can have a total amine value of at least150, at least 175, at least 185, at least 250, or at least 280, aprimary amine value of at least 100, such as at least 135, at least 150,at least 165, or at least 175, and optionally a secondary amine value ofat least 100, such as at least 135. Examples are available from HumKoChemical of Memphis, Tenn. Fatty polyamine telechelics can be branched,such as with alkyl groups, suitable in forming soft segments, and informulating solvent-free two pack full solid polyurethane/polyureacompositions. Fluid fatty polyamine telechelics can be used as reactivediluents in solvent-borne polyurethane/polyurea compositions to achievehigher solid content. Conventional volatile solvents such as xylene,butyl acetate, methoxy propylacetate, ethoxy propylacetate may be usedin blends thereof.

j) Polyamine Telechelics Derived from Acid-Catalyzed Polyol Telechelics

Polyamines and/or polyamine telechelics can be derived from theacid-catalyzed polyols and/or polyol telechelics of the presentdisclosure, such as having the structure of R₁HN—[R—O—]_(n)—R—NHR₂,where R₁ and R₂ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R is a linear orbranched alkylene radical having about 5 carbon atoms or more, such asabout 8, about 10, about 12, about 16, about 18, about 20, about 30,about 36, about 44, and about 54 carbon atoms or more; and n is morethan 1, such as about 2 or more. The main chain of R can have at leastabout 5 carbon atoms, such as about 8 or about 10 carbon atoms or more.For molecularly non-uniform polyamine polyethers, the number n can beabout 0.5-5, such as about 1-4. For molecularly uniform polyaminepolyethers, the number n can be about 1-10, such as about 3-6. Thepolyamine polyethers can have an acid value of less than 5, such asabout 1-3, and a viscosity at 25° C. of about 3,000 cP or greater, suchas about 3,800-12,000 cP.

k) Polyamine Polyethercarbonates

Polyamine polyethercarbonates can be derived from thecarbonate-transesterified polyol telechelics as disclosed herein, havingM_(w) of about 500-12,000, such as about 700, about 1,000, about 2,000,about 2,500, about 3,000, about 5,000, about 6,000, or any numbertherebetween, in which a ratio of ether linkages to carbonate linkagesis about 5:1 to about 1:5, such as about 3:1 to about 1:3, and thevarious alkylene units are arranged statistically, alternately, and/orblockwise. Some of these polyamine polyethercarbonates can below-melting waxes, having a softening point of less than about 40° C.,and a viscosity at 50° C. of about 8,500 or less, such as about 5,000,about 3,500, about 2,000, about 600, or less, or any numbertherebetween. Some of these polyamine polyethercarbonates can be liquidat room temperature. These polyamine polyethercarbonates can be high inhydrophobicity, hydrolysis resistance, and saponification resistance.

l) Derivatized Polyamine Telechelics

Polyamine telechelics can be derived from corresponding polyacids, suchas by reacting the polyacids with ammonia to obtain the correspondingnitriles which may then be hydrogenated to form the polyaminetelechelics. Polyamine telechelics can also be derived fromcorresponding polyol telechelics through, for example, amination,reaction with suitable amino acids or esters thereof, reaction withsuitable cyclic amides, or reaction with suitable polyamines oraminoalcohols. Amination, as understood by one of ordinary skill in theart, includes reductive amination of polyether polyols with ammonia andhydrogen in the presence of a catalyst, hydrogenation of cyanoethylatedpolyols, amination of polyol/sulfonic acid esters, reacting polyols withepichlorohydrin and a primary amine, and any other methods known to theskilled artisan. Fatty polyacids and polyacid adducts such as thedimerized fatty acids as disclosed herein can be converted to fattypolyamines and dimer diamines through one or more of these mechanisms.When cyclic amides are used to form the polyamine telechelics, thenon-carbonyl carbon adjoining N can be substituted with at least onecyclic structure (e.g., cyclic hydrocarbons, heterocyclics) or at leasttwo organic moieties selected from halides and C₁ to C₂₀ linear orbranched aliphatic moieties.

The amino acids or esters thereof used to form the polyamine telechelicscan have a generic structure of R′₁HN-Z′-COOR′₂, where R′₁ and R′₂ areindependently chosen from hydrogen, aliphatic, araliphatic,cycloaliphatic, and aromatic moieties; and Z′ is a divalent organicmoiety. R′₁ and R′₂ can be linear or branched structures having about 20carbon atoms or less, such as 1-12 carbon atoms. The amino acids oresters thereof can react with polyol telechelics to form polyaminetelechelics having ester linkages. In one example, the polyol telecheliccan be a polyol polyether, and the derived polyamine telechelic can be apolyamine polyetherester having a generic structure of:

where R′¹, R′₂, and Z′ are as described above, R is chosen fromhydrogen, linear or branched alkyl group (such as methyl), phenyl group,halide, and mixture thereof, n is about 1-12, and x is about 1-200. Suchpolyamine polyetheresters can be obtained by end-capping polyolpolyethers with 4-aminobenzoic acid and methyl or ethyl esters thereof,e.g., poly(1,4-butanediol)-bis(4-aminobenzoate) in liquid or waxy solidform, polyethyleneglycol-bis(4-aminobenzoate), polytetramethylene etherglycol-di-p-aminobenzoate, polypropyleneglycol-di-p-aminobenzoate, andmixtures thereof.

The reactivity of the reactive amine end-groups in polyamine telechelicscan be moderated to improve molecular stability of the resultingproducts toward actinic radiations such as UV light, by means of, forexample, increasing steric hinderance around these amine end-groups. Toimpart hightened steric hinderance, the amino acids or esters of thegeneric structure above can have at least one branched aliphatic orsubstituted cyclic structure in Z′, wherein at least one structuralcondition chosen from the following is met: i) both R′₁HN and COOR′₂adjoin a single carbon atom; ii) R′₁HN adjoins a tertiary carbon atom inZ′, iii) R′₁HN adjoins a secondary carbon atom (such as a methinecarbon) in Z′, the secondary carbon being further adjoined to two othercarbon atoms selected from tertiary and quaternary carbons; and iv)R′₁HN adjoins a secondary carbon atom in Z′, the secondary carbon beingfurther adjoined to a quaternary carbon atom that adjoins COOR′₂.Generic structures of such amino acids or esters thereof include thefollowing:

where R′₁ and R′₂ are as described above; R₁, R₂, R₄, and R₅ areindependently chosen from linear or branched C₁ to C₆₀ organic moieties,such as C₁ to C₂₀ aliphatic hydrocarbon moieties, or C₁ to C₁₂ alkylgroups; R₃ is linear or branched C₁ to C₆₀ organic moiety, such as C₁ toC₂₀ aliphatic hydrocarbon moiety, or C₁ to C₁₂ alkylene moiety; R₆ andR₇ are the same or different linear or branched, substituted orunsubstituted, organic moieties having about 20 carbon atoms or less,such as C₁ to C₁₂ aliphatic hydrocarbon moieties, or C₁ to C₄ alkylenemoieties; and x, y, and z are independently 0 or 1. R′₁ and R₁ to R₇ mayindependently be linear or branched, substituted (such as halogenated)or unsubstituted, have one or more heteroatoms such as O, N, S, P, orSi, and/or have one or more cyclic structures. Suitable cyclicstructures can be substituted or unsubstituted, saturated orunsaturated, having five or more ring members, three or more of whichcan be carbon atoms, and include monocyclics, polycyclics (fused, spiro,and/or bridged), and heterocyclics. A non-limiting example of suitableamino acids is 1-aminocyclopentane carboxylic acid.

One group of polyamine telechelics can be derived from the derivatizedpolyol telechelics as disclosed herein, thereby having ring-openedcyclic ether moieties at the termini attaching to the amine end-groups.General structure of such telechelics can beR₁HN—(Y—O)_(m)—X—O-(Z-O)_(n)—NHR₂, where R₁ and R₂ are independentlychosen from hydrogen, alkyl, aryl, aralkyl, alicyclic, cycloalkyl, andalkoxy groups; X is the backbone of the starting polyol telechelicHO-Z-OH; Y is the organic moiety of cyclic ether

Z is the organic moiety of cyclic ether

m and n are the same or different numbers of 0 or more, and m+n is about2-100, such t about 2-40. Y and Z can be the same or different, and canhave 2 or more carbon atoms or 5 or more carbon atoms. Y and Z canindependently have one or more heteroatoms such as O, S, N, and Si. Themolecular weight of segment Z-O can be at least about 1% by weight ofthe M_(w) of the polyamine telechelic, the latter of which can be about500-20,000, such as about 600, about 1,000, about 2,000, about 3,000,about 5,000, about 8,000, about 10,000, about 12,000, about 15,000, andany number therebetween.m) Ethylenically and/or Acetylenically Unsaturated Polyamine Telechelics

Any of the polyamine telechelics disclosed herein above may compriseone, two, or a plurality of ethylenic and/or acetylenic unsaturationmoieties. These unsaturation moieties can be used to form carbon-carbonand/or ionic crosslinks in combination with vulcanizing agents (i.e.,radical initiators, polyisocyanates, co-crosslinking agents, curativescomprising ethylenic and/or acetylenic unsaturation moieties, and/orprocessing aids). These unsaturation moieties may be pendant along thebackbone of the polyamine telechelics, attached to pendant groups orchains branched off the backbone, and/or attached to the amineend-groups of the polyamine telechelics.

For example, ethylenically and/or acetylenically unsaturated polyaminepolyhydrocarbons include, without limitation, those having high or lowvinyl polyolefin backbones. These backbones can be formed from one ormore diene monomers, optionally with one or more other hydrocarbonmonomers. Exemplary diene monomers include conjugated dienes containing4-12 carbon atoms, such as 1,3-butadiene, isoprene, chloroprene,2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene,3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene,phenyl-1,3-butadiene, and the like; non-conjugated dienes containing5-25 carbon atoms such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene,2,5-dimethyl-1,5-hexadiene, 1,4-octadiene, and the like; cyclic dienessuch as cyclopentadiene, cyclohexadiene, cyclooctadiene,dicyclopentadiene, and the like; vinyl cyclic enes such as1-vinyl-1-cyclopentene, 1-vinyl-1-cyclohexene, and the like;alkylbicyclononadienes such as 3-methylbicyclo-(4,2,1)-nona-3,7-diene,and the like, indenes such as methyl tetrahydroindene, and the like;alkenyl norbornenes such as 5-ethylidene-2-norbornene,5-butylidene-2-norbornene, 2-methallyl-5-norbornene,2-isopropenyl-5-norbornene, 5-(1,5-hexadienyl)-2-norbornene,5-(3,7-octadienyl)-2-norbornene, and the like; and tricyclodienes suchas 3-methyltricyclo (5,2,1,0^(2,6))-deca-3,8-diene and the like.

Non-limiting examples of vinyl polyolefin backbones are vinylpolybutadienes, vinyl polyisoprenes, vinyl polystyrenebutadienes, vinylpolyethylenebutadienes, vinyl poly(styrene-propylene-diene)s, vinylpoly(ethylene-propylene-diene)s, and fluorinated or perfluorinatedderivatives thereof. High 1,2-vinyl content can be at least about 40%,such as 50%, 60%, 70%, 80%, 90%, or even greater. Low 1,2-vinyl contentcan be less than about 35%, such as 30%, 20%, 15%, 12%, 10%, 5%, or evenless. The vinyl polyolefin backbone can have various combinations ofcis-, trans-, and vinyl structures, such as having a trans-structurecontent greater than cis-structure content and/or 1,2-vinyl structurecontent, having a cis-structure content greater than trans-structurecontent and/or 1,2-vinyl structure content, or having a 1,2-vinylstructure content greater than cis-structure content or trans-structurecontent.

Other ethylenically and/or acetylenically unsaturated moieties that maybe incorporated onto the backbone of the polyamine telechelics includeallyl groups and α,β-ethylenically unsaturated C₃ to C₈ carboxylategroups. Non-limiting examples of such ethylenically unsaturated moietiesinclude acrylate, methacrylate, fumarate, β-carboxyethyl acrylate,itaconate, and others unsaturated carboxylates disclosed herein. Theseunsaturated moieties can attach to the amine groups on the polyaminetelechelics by forming amide linkages. The incorporation of theseunsaturated moieties may take place before the formation of prepolymer,or after the prepolymer is reacted with stoichiometrically excessiveamounts of polyamine and/or polyol curatives.

Ethylenically and/or acetylenically unsaturated polyaminepolyhydrocarbons can be liquid at ambient temperature, such as thosehaving vinyl polybutadiene homopolymers or copolymers as backbones, andcan have low to moderate viscosity, low volatility and emission, highboiling point (such as greater than 300° C.), and molecular weight ofabout 1,000 to about 5,000, such as about 1,800 to about 4,000, or about2,000 to about 3,500.

Polyamines

Polyamines suitable for use in the present disclosure include any andall organic compounds having two, three, four, or more amine groups inthe molecule that are capable of forming urea linkages (such as withisocyanate groups) or amide linkages (such as with carboxyl group). Thepolyamine can be aromatic, araliphatic, aliphatic, alicyclic,heterocyclic, saturated or unsaturated, and each molecule has at leasttwo isocyanate-reactive amine groups independently being primary orsecondary. Depending on the number of isocyanate-reactive amine groupsbeing present, polyamines may be referred to as diamines, triamines,tetramines, and other higher polyamines.

a) Aromatic Polyamines

Aromatic polyamines may have one or more monocyclic or aromaticpolycyclic (fused, spiro, and/or bridged) aromatic rings, where at leasttwo isocyanate-reactive amine groups are directly attached to the rings.Aromatic polyamines can have about 6-60 carbon atoms, such as about 6-22carbon atoms. Non-limiting examples of single-ring aromatic diaminesinclude o-, m-, or p-phenylenediamine, 1,2-, 1,3-, or1,4-bis(sec-butylamino) benzene, toluene diamine, 3,5-diethyl-(2,4- or2,6-)toluenediamine, 3,5-dimethylthio-(2,4- or 2,6-)toluenediamine, and3,5-diethylthio-(2,4- or 2,6-)toluenediamine. Illustrative examples offused polycyclic aromatic diamines are 1,4-, 1,6-, 1,8-, and2,7-diaminonaphthalene.

Non-limiting examples of dual-ring aromatic polyamines include4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane (“MDA”),4,4′-diaminodiphenylpropane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane,3,3′-diethyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane,3,3′-dichloro-4,4′-diaminodiphenylmethane (“MOCA”),3,3′-diethyl-5,5′-dichloro-4,4′-diaminodiphenylmethane,3,3′,5,5′-tetraethyl-4,4′-diaminodiphenylmethane (“MDEA”),3,3′,5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane,3,3′-dimethyl-5,5′-diisopropyl-4,4′-diaminodiphenylmethane,3,3′-diethyl-5,5′-diisopropyl-4,4′-diaminodiphenylmethane,3,3′-dimethyl-5,5′-di-t-butyl-4,4′-diaminodiphenylmethane,2,2′-dichloro-3,3′,5,5′-tetraethyl-4,4′-diaminodiphenylmethane(“MCDEA”), 3,3′-dichloro-4,4′-diaminodiphenylmethane,2,2′,3,3′-tetrachloro-4,4′-diaminodiphenylmethane (“MDCA”),3,3′-dichloro-2,2′,6,6′-tetraethyl-4,4′-diaminodiphenylmethane,4,4′-bis(sec-butylamino)-diphenylmethane, andN,N′-dialkylamino-diphenylmethane.

b) Araliphatic Polyamines

Araliphatic polyamines may have one or more monocyclic or polycyclic(fused, spiro, and/or bridged) aromatic rings having substitutedaliphatic chains, where at least two isocyanate-reactive amine groupsare attached to the aliphatic chains rather than the aromatic rings.Araliphatic polyamines can have about 6-60 carbon atoms, such as about6-22 carbon atoms. Non-limiting examples of araliphatic polyaminesinclude aminoalkylbenzenes such as o-, m-, or p-xylylenediamine.

c) Aliphatic Polyamines

Aliphatic polyamines have a linear or branched, saturated orunsaturated, substituted or unsubstituted primary aliphatic chain,optionally having heteroatoms such as N, O, S, or Si present in theprimary chain, where at least two isocyanate-reactive amine groups areattached to the primary chain or side chains or pendant moietiesbranching off the primary chain. Aliphatic polyamines can have about 60carbon atoms or less, such as about 2-30 carbon atoms. Non-limitingexamples of aliphatic diamines include primary diamines such as ethylenediamine, 1,3-propylene diamine, 2-methyl-pentamethylene diamine,1,3-pentanediamine, neopentyldiamine, hexamethylene diamine, 2,2,4- and2,4,4-trimethyl-1,6-hexane diamine, imino-bis(propylamine),methylimino-bis(propylamine) (i.e.,N-(3-aminopropyl)-N-methyl-1,3-propanediamine,N,N-bis(aminopropyl)methylamine), N,N-bis(aminopropyl)ethylamine,N,N-bis(aminopropyl)hexylamine, and N,N-bis(aminopropyl)octylamine;secondary diamines such as N,N′-diethylmaleate-2-methyl-pentamethylenediamine (Desmophen® NH 1220); primary/secondary diamines such as2-(ethylamino)ethylamine, 3-(methylamino)propylamine, andN,N-dimethyldipropylenetriamine. Other aliphatic polyamines, such asfatty polyamines, alkylene polyamines, alkoxylated diamines, hydroxypolyamines, and condensed polyamines are disclosed in detail herein.

d) Alicyclic Polyamines

Alicyclic polyamines may have one or more carbon-based, saturated orhydrogenated, monocyclic or polycyclic (fused, spiro, and/or bridged)rings, optionally having substituted aliphatic chains on the rings orlinking multiple rings, where at least two isocyanate-reactive aminegroups are attached to the rings and/or the aliphatic chains. Alicyclicpolyamines can have about 6-60 carbon atoms, such as about 6-30 carbonatoms. Non-limiting examples of alicyclic diamines include monocyclicssuch as 1,2-, 1,3-, or 1,4-diamino-cyclohexane,1-methyl-2,6-diamino-cyclohexane, 1,3- or1,4-bis(methylamino)-cyclohexane, 1,2-, 1,3-, or1,4-bis(aminomethyl)cyclohexane, 1,2- or1,4-bis(sec-butylamino)-cyclohexane, isophorone diamine, andN,N′-diisopropyl-isophorone diamine (Jefflink® 754); and polycyclicssuch as 2,2′-, 2,4′-, or 4,4′-diamino-dicyclohexylmethane,3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane (i.e., dimethyl dicykan),3,3′-diethyl-5,5′-dimethyl-4,4′-diamino-dicyclohexylmethane,3,3′-dichloro-4,4′-diamino-dicyclohexylmethane,3,3′-diethyl-5,5′-dichloro-4,4′-diamino-dicyclohexylmethane,3,3′,5,5′-tetraethyl-4,4′-diamino-dicyclohexylmethane (a.k.a.4,4′-methylene-bis(2,6-diethylaminocyclohexane)),2,2′-dichloro-3,3′,5,5′-tetraethyl-4,4′-diamino-dicyclohexylmethane,3,3′-dichloro-4,4′-diamino-dicyclohexylmethane,2,2′,3,3′-tetrachloro-4,4′-diamino-dicyclohexylmethane,3,3′-dichloro-2,2′,6,6′-tetraethyl-4,4′-dicyclohexylmethane,4,4′-bis(sec-butylamino)-dicyclohexylmethane (Clearlink® 1000),N,N′-dialkylamino-dicyclohexylmethane,3,3′-dimethyl-4,4′-bis(sec-butylamino)-dicyclohexylmethane (Clearlink®3000), N,N′-di(ethylmaleate-amino)-dicyclohexylmethane (Desmophen® NH1420), N,N′-di(ethylmaleate-amino)-dimethyl-dicyclohexylmethane(Desmophen® 1520), 4,4′-diamino-dicyclohexylpropane, 2,5- or2,6-bis(aminomethyl)norbornane, and bis(aminomethyl)tricyclodecane (TCDdiamine),

e) Heterocyclic Polyamines

Heterocyclic polyamines may have one or more saturated or unsaturated,monocyclic or polycyclic (fused, spiro, and/or bridged) rings having oneor more heteroatoms, such as O, N, and S, optionally having substitutedaliphatic chains on the rings or linking multiple rings, where at leasttwo isocyanate-reactive amine groups are attached to the rings and/orthe aliphatic chains, or in part form the rings. Heterocyclic polyaminescan have about 4-60 carbon atoms, such as about 4-30 carbon atoms, andinclude aziridines, azetidines, azolidines, pyridines, pyrroles,indoles, piperidines, imidazoles, imidazolines, piperazines, isoindoles,purines, morpholines, thiomorpholines, oxazolidines, thiazolidines,N-aminoalkylmorpholines, N-aminoalkylthiomorpholines,N-aminoalkylpiperazines, N,N′-diaminoalkylpiperazines, azepines,azocines, azonines, azecines, tetra-, di- and perhydro derivativesthereof, and mixtures of two or more thereof. Saturated 5- and6-membered heterocyclic polyamines can comprise only N, O, and/or S inthe hetero ring, such as piperidines, piperazines, thiomorpholines,morpholines, pyrrolidines, aminoalkyl-substituted derivatives thereof,and the like. The aminoalkyl substituents can be substituted on anitrogen atom forming part of the hetero ring.

Non-limiting examples of heterocyclic diamines include piperazine,N-(aminoalkyl)piperazine, N-(aminoethyl)piperazine,N-(aminopropyl)piperazine, bis(aminoalkyl)piperazine,bis(aminoethyl)piperazine, bis(aminopropyl)piperazine, 2-, 3-, or4-aminomethyl-piperidine, aminoethylpiperazine, aminopropylpiperazine,bis(piperidyl)alkane, 1,3-di(4-piperidyl)propane, 3-amino-pyrrolidine,homopiperazine, 2-methyl-piperazine, cis-2,6-dimethyl-piperazine,2,5-dimethyl-piperazine, N-(2-imidazole)piperazine, histamine (i.e.,4-(β-aminoethyl)imidazole), N-(aminoethyl)imidazole,N-(aminopropyl)imidazole, and N-aminopropylmorpholine.

f) Triamines, Tetramines, and Higher Polyamines

Non-limiting examples of triamines include diethylene triamine,dipropylene triamine, N-(aminopropyl)ethylenediamine,N-(aminoethyl)butylenediamine, N-(aminopropyl)butylenediamine,N-(aminoethyl)hexamethylenediamine, N-(aminopropyl)hexamethylenediamine,4-aminomethyloctane-1,8-diamine, (propylene oxide)-based triamines(a.k.a. polyoxypropylene triamines), trimethylolpropane-based triamines,glycerin-based triamines, 3-(2-aminoethyl)aminopropylamine (i.e.,N-(2-aminoethyl)-1,3-propylenediamine, N₃-amine),N,N-bis(2-((aminocarbonyl)amino)ethyl)urea,N,N′,N″-tris(2-aminoethyl)methanetriamine,N1-(5-aminopentyl)-1,2,6-hexanetriamine, 1,1,2-ethanetriamine,N,N′,N″-tris(3-aminopropyl)methanetriamine,N1-(2-aminoethyl)-1,2,6-hexanetriamine,N1-(10-aminodecyl)-1,2,6-hexanetriamine, 1,9,18-octadecanetriamine,4,10,16,22-tetraazapentacosane-1,13,25-triamine,N1-(3-((4-((3-aminopropyl)amino)butyl)amino)propyl)-1,2,6-hexanetriamine,di-9-octadecenyl-(Z,Z)-1,2,3-propanetriamine, 1,4,8-octanetriamine,1,5,9-nonanetriamine, 1,9,10-octadecanetriamine, 1,4,7-heptanetriamine,1,5,10-decanetriamine, 1,8,17-heptadecanetriamine, 1,2,4-butanetriamine,1,3,5-pentanetriamine,N1-(4-((3-aminopropyl)amino)butyl)-1,2,6-hexanetriamine,2,5-dimethyl-1,4,7-heptanetriamine,N1-6-aminohexyl-1,2,6-hexanetriamine,6-ethyl-3,9-dimethyl-3,6,9-undecanetriamine, 1,5,11-undecanetriamine,1,6,11-undecanetriamine, N,N-bis(aminomethyl)methanediamine,N,N-bis(2-aminoethyl)-1,3-propanediamine, methanetriamine,N1-(2-aminoethyl)-N2-(3-aminopropyl)-1,2,5-pentanetriamine,N1-(2-aminoethyl)-1,2,6-hexanetriamine,2,6,11-trimethyl-2,6,11-dodecanetriamine, 1,1,3-propanetriamine,6-(aminomethyl)-1,4,9-nonanetriamine, 1,2,6-hexanetriamine,N2-(2-aminoethyl)-1,1,2-ethanetriamine, 1,3,6-hexanetriamine,N,N-bis(2-aminoethyl)-1,2-ethanediamine,3-(aminomethyl)-1,2,4-butanetriamine, 1,1,1-ethanetriamine,N1,N1-bis(2-aminoethyl)-1,2-propanediamine, 1,2,3-propanetriamine, and2-methyl-1,2,3-propanetriamine (all saturated). Non-limiting examples oftetramines include triethylene tetramine (i.e.,bis(aminoethyl)ethylenediamine), tetraethylene tetramine, tripropylenetetramine, N,N′-bis(3-aminopropyl)ethylenediamine (a.k.a. N₄-amine,N,N′-1,2-ethanediylbis-(1,3-propanediamine), 1,5,8,12-tetrazadodecane),bis(aminoethyl)propylenediamine, bis(aminoethyl)butylenediamine,bis(aminopropyl)butylenediamine, bis(aminoethyl)hexamethylenediamine,bis(aminopropyl)hexamethylenediamine. Illustrative examples of otherhigher polyamines include tetraethylene pentamine (also saturated).pentaethylene hexamine, polymethylene-polyphenylamine.

g) Fatty Polyamines

Fatty polyamines can have in the main carbon chain at least about 8carbon atoms (including carbon atom(s) in the carboxylic acid group(s),if directly attached to the main carbon chain), such as 10, 12, 16, 18,20, 22, 28, 30, 36, 40, 44, 50, 54, or 60 carbon atoms, or any numberstherebetween. The main carbon chain can be directed attached to at leastone, such as two or more, isocyanate-reactive amine functionality, whichcan be primary and/or secondary. The fatty polyamines can be monomerdiamines, dimer diamines or trimer triamines derived from fattypolyacids disclosed herein, using textbook techniques such as byreacting the dimerized fatty acids with ammonia to obtain thecorresponding dimerized fatty nitriles which may then be hydrogenated toform the dimer diamines.

The fatty polyamines can have the formula R₁—(NH—R₂)_(x)—NH₂ where R₁ isa linear or branched alkyl group having about 8-40 carbon atoms, such asabout 10-35 carbon atoms, or about 12-18 carbon atoms; R₂ is a divalentmoiety having 1 to about 8 carbon atoms, such as about 2-6 carbon atoms,or about 2-4 carbon atoms; and x is about 1-6, such as about 1-4. R₁ andR₂ can be linear or branched, saturated or unsaturated, or combinationthereof. R₁ can be chosen from linear decyl, dodecyl, hexadecyl andoctadecyl, R₂ can be ethylene or propylene, and x is about 1-3. Thesefatty polyamines may be prepared by conventional methods, such assequential cyanoethylation reduction reactions. Commercially availableexamples include those with R₁ being octadecyl, R₂ being propylene, andx being 1, 2 or 3 (tallow diamine, tallow triamine, and tallowtetramine, respectively), available from ExxonMobil Chemical Company ofHouston, Tex.

h) Alkylene Polyamines

Alkylene polyamines are represented by the formula RHN—[R′—N(R)]_(x)—H,where each R is independently hydrogen, aliphatic, orhydroxy-substituted aliphatic group of up to about 30 carbon atoms; R′is alkylene moiety having about 1-10 carbon atoms, such as about 2-6carbon atoms, or about 2-4 carbon atoms; n is about 1-10, such as about2-7 or about 2-5. Such alkylene polyamines include methylene polyamines,ethylene polyamines, propylene polyamines, butylene polyamines,pentylene polyamines, etc. The higher homologs, such as those obtainedby condensing two or more alkyleneamines, and related heterocyclicamines, such as piperazines and N-amino alkyl-substituted piperazines,are also included.

Alkylene polyamines such as ethylene polyamines can be a complex mixtureof polyalkylene polyamines including cyclic condensation products. Theterm “polyalkylene polyamine” as employed herein is intended to includepolyalkylene polyamines in pure or relatively pure form, mixtures ofsuch materials, and crude polyalkylene polyamines, which may containminor amounts of other compounds. Other useful types of polyaminemixtures are those resulting from stripping of the polyalkylenepolyamine mixtures to leave, as residue, what is often termed “polyaminebottoms.” In general, alkylene polyamine bottoms can be characterized ashaving less than 2%, usually less than 1% (by weight) material boilingbelow about 200° C. These alkylene polyamine bottoms include cycliccondensation products such as piperazine and higher analogs ofdiethylenetriamine, triethylenetetramine and the like. These alkylenepolyamine bottoms may be reacted solely with the acylating agent or theymay be used with other amines, polyamines, or mixtures thereof.

Specific examples of such polyamines are ethylenediamine,diethylenetriamine, triethylenetetramine, tris-(2-aminoethyl)amine,propylenediamine, dipropylenetriamine, tripropylenetetramine,tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine,N-(2-aminoethyl)piperazine, N,N-bis(2-aminoethyl)-ethylenediamine,diaminoethyl triaminoethylamine, and the like. The correspondingpolypropylene polyamines and the polybutylene polyamines can also beemployed. Still other polyamines can be recognized by those skilled inthe art and the present disclosure can be used with such polyamines.

i) Condensate Polyamines

Polyamines can be condensation reaction products of at least one hydroxycompound with at least one polyamine reactant containing two or moreprimary and/or secondary amine groups. The hydroxy compound includespolyols and polyol amines disclosed herein. Polyol amines includeaminoalcohols having two or more hydroxyl groups, and reaction productsof monoamines with alkylene oxides (e.g., ethylene oxide, propyleneoxide, butylene oxide, etc.) having about 2-20 carbon atoms, such asabout 2-4 carbon atoms. Non-limiting examples of polyol amines includetri(hydroxypropyl)amine, tris(hydroxymethyl)aminomethane (THAM),2-amino-2-methyl-1,3-propanediol,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, andN,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine.

Any polyamines of the present disclosure may react with the polyols andpolyol amines to form the condensate polyamines. Non-limiting examplesinclude triethylenetetramine (TETA), tetraethylenepentamine (TEPA),pentaethylenehexamine (PEHA), and mixtures of polyamines such as thealkylene polyamine bottoms. The condensation reaction can be conductedat about 60-265° C., such as about 220-250° C., in the presence of anacid catalyst. Materials and conditions to form the condensatepolyamines are described in U.S. Pat. No. 5,230,714, the disclosure ofwhich is incorporated herein by reference.

k) Other Polyamines

Hydrazine and hydrocarbyl-substituted hydrazine may also be used aspolyamines. At least one of the nitrogen atoms in the hydrazine maycontain at least one hydrogen directly bonded thereto. There can be atleast two hydrogen atoms bonded directly to hydrazine nitrogen, and bothhydrogen atoms can be on the same nitrogen. Non-limiting examples ofsubstituted hydrazines are methylhydrazine, N,N-dimethyl hydrazine,N,N′-dimethyl hydrazine, phenylhydrazine, N-phenyl-N′-ethylhydrazine,N-(p-tolyl)-N′-(n-butyl)-hydrazine, N-(para-nitrophenyl)-hydrazine,N-(para-nitrophenyl)-N-methylhydrazine,N,N′-di(p-chlorophenol)-hydrazine, and N-phenyl-N′-cyclohexylhydrazine.

j) Sterically Hindered Polyamines

Conventional polyamines can be fast reacting with isocyanates. In orderto extend the pot-life of the composition and improve processability,polyamine reactivity may be moderated by sterically hinder the reactiveamine groups. For example, 4,4′-bis-(sec-butylamino)-dicyclohexylmethaneand N,N′-diisopropyl-isophorone diamine are secondary diamines havingmoderated reactivity.

One or more or all of the reactable amine groups within the polyaminecompound can be sterically hindered, so that the polyamine compound canprovide the combination of reduced reactivity toward isocyanate groups,and improved chemical stability toward actinic radiations such as UVlight. Sterically hindered NCO group can have the following structure:

where C₁, C₂, and C₃ are independent tertiary (i.e., methine) orquaternary carbon atoms, and R is as defined above. One, two, or allthree of C₁, C₂, and C₃ can be free of C—H bonds. C₁, C₂, and C₃ may inpart form a substituted ring structure having about 4-30 carbon atoms.The ring structure may be saturated, unsaturated, aromatic, monocyclic,polycyclic (e.g., bicyclic, tricyclic, etc.), or heterocyclic having oneor more O, N, or S atoms. The ring structure may have one, two, three,or more moieties of the above structure, while the polyamine compoundmay have one, two, or more of such ring structures. For example,sterically hindered polyamine may have a structure of:

where Z₁ to Z₈ are independently chosen from halogenated orun-halogenated hydrocarbon moieties having about 1-20 carbon atoms,halogenated or un-halogenated organic moieties having at least one O, N,S, or Si atom and zero to about 12 carbon atoms, or halogens; Y₁ to Y₄are independently chosen from hydrogen, halogenated or un-halogenatedhydrocarbon moieties having about 1-20 carbon atoms, halogenated orun-halogenated organic moieties having at least one O, N, S, or Si atomand zero to about 12 carbon atoms, and halogens; Z is halogenated orun-halogenated hydrocarbon moieties having about 1-60 carbon atoms, orhalogenated or un-halogenated organic moieties having at least one O, N,S, or Si atom and zero to about 60 carbon atoms. Z can have one of thefollowing structures:

where A₁ to A₃ are independently chosen from halogenated orun-halogenated hydrocarbon moieties having about 1-36 carbon atoms, andhalogenated or un-halogenated organic moieties having at least one O, N,S, or Si atom and zero to about 30 carbon atoms. Any one or more, or allof Z₁ to Z₈ can be hydrogen. As a non-limiting example, Z may be—C(CH₃)₂—. Other non-limiting examples include 1,4-durene diamine,2,3,5,6-tetramethyl-1,4-diaminocyclohexane, and:

where R is the same or different, chosen from hydrogen and linear orbranched C₁-C₆ alkyl groups, such as methyl, ethyl, propyl, butyl,pentyl, hexyl, iso-propyl, iso-butyl, sec-butyl, neo-pentyl, and maleategroups.

Sterically hindered polyamines can also have a generic structure of:

where R₁, R₂ and Z₁ to Z₄ are independently chosen from hydrogen andorganic moieties having about 1-60 carbon atoms, such as about 1-20,about 1-12, or about 1-6 carbon atoms. Suitable organic moieties can belinear or branched, saturated or unsaturated, aliphatic, alicyclic,aromatic, or araliphatic, halogenated or otherwise substituted,optionally having one or more heteroatoms such as O, N, S, or Si, andinclude hydrocarbon moieties such as alkyl, alkyloxy, alkylthio, oralkylsilyl moieties. NHR, and NHR₂ can be in ortho, meta, or parapositions with respect to one another. One or more of Z₁ to Z₄ can beNHR₃, where R₃ is analogous to R₁ and R₂.

In one example, R₁ and R₂ are both hydrogen, and at least one of Z₁ toZ₄, such as two or more thereof, is/are the organic moieties describedabove, having 2 or more carbon atoms, or being branched and having 3 ormore carbon atoms. In another example, at least one of R₁ and R₂ can bethe organic moiety other than hydrogen, having 2 or more carbon atoms,such as being branched and having 3 or more carbon atoms. In a furtherexample, at least one of R₁, R₂, and Z₁ to Z₄ can have one or moreprimary or secondary amine groups, such as one or more primary amineend-groups distal to the ring structure. In yet another example, thesterically hindered polyamine can be regioselective; that is, at least afirst amine group has a reactivity different from that of a second aminegroup, all else being equal. The regioselectivity may result fromdifference in steric interference around the two different amine groups(i.e., steric asymmetry). Scenarios which may result in regioselectivityinclude: a) the first amine is secondary, while the second amine isprimary; b) the first amine is sterically hindered by one or moreortho-positioned organic moieties, on one side or both sides, while thesecond amine has none; or c) the first amine is sterically hindered bytwo or more ortho-positioned organic moieties on both sides, while thesecond amine has only one ortho-positioned organic moiety.

Sterically hindered dual- or multi-ring polyamines can have a genericstructure of:

where R is the same or different on different rings, chosen fromhydrogen and organic moieties having about 20 carbon atoms or less, suchas 1-12 carbon atoms; Z₁ to Z₄, each being the same or different ondifferent rings, are independently chosen from hydrogen, halides, andorganic moieties having 1-12 or 1-6 carbon atoms; Z is a divalent orpolyvalent organic moiety having a molecular weight of at least about14, such as about 5,000 or less, or about 1,000 or less; m is 2 when nis 0, about 2-6 when n is 1, such as 2, 3, or 4. Organic moieties for R,Z, and Z₁ to Z₄ can be linear or branched, saturated or unsaturated,aliphatic, alicyclic, aromatic, or araliphatic, halogenated or otherwisesubstituted, optionally having one or more heteroatoms such as O, N, S,or Si, such as hydrocarbon moieties. Z may be as small as O or CH₂, orcomprise polymeric chains such as polyhydrocarbon, polyether, polyester,polyamide, polycarbonate, polyacrylate, polysiloxane, and copolymerchains thereof. Alternatively, Z may comprise at least two ester and/oramide linkages.

In one example, R is hydrogen, at least one of Z₁ to Z₄, such as two ormore thereof, is/are the organic moieties described above, such ashaving two or more carbon atoms, or branched having 3 or more carbonatoms, and is/are ortho to NHR. In another example, each NHR is anortho- or meta-substituent with respect to Z. In a further example, atleast one R is an organic moiety, such as having 2 or more carbon atoms,or branched having 3 or more carbon atoms. In yet another example, atleast one of R and Z₁ to Z₄ has one or more primary or secondary aminegroups, such as at least one primary amine end-group distal to the ring.In still another example, the sterically hindered polyamine isregioselective, having one of the following scenarios: i) a first NHR issecondary, while a second NHR is primary; ii) the first NHR issterically hindered by one or more ortho-positioned organic moieties onone side or both sides, while the second NHR has none; or iii) the firstNHR is sterically hindered by two or more ortho-positioned organicmoieties one both sides, while the second NHR has onlyone-ortho-positioned organic moiety.

Certain sterically hindered polyamines described above can be obtainedby reacting one or more ortho- or meta-isomers of cyclic amino acids oresters thereof, such as (organo)amino(organo)benzene (organo)acids(including aminobenzoic acids, aminobenzene organoacids,amino-organobenzoic acids, organo-aminobenzoic acids,amino-organobenzene organoacids, organo-aminobenzene organoacids,organo-amino-organobenzoic acids, and organo-amino-organobenzeneorganoacids), (organo)amino(organo)cyclohexane (organo)acids (includingaminocyclohexane acids, aminocyclohexane organoacids,amino-organocyclohexane acids, organo-aminocyclohexane acids,amino-organocyclohexane organoacids, organo-aminocyclohexaneorganoacids, organo-amino-organocyclohexane acids, andorgano-amino-organocyclohexane organoacids), and their respective esters(such as methyl esters, ethyl esters, propyl esters, isopropyl esters,butyl esters, isobutyl esters, t-butyl esters, pentyl esters, hexylesters, and other linear and branched alkyl esters known to one skilledin the art), with one or more compounds having two or more activehydrogen functionalities (e.g., the various amine- and/orhydroxy-functional compounds and telechelics disclosed herein). Activehydrogen functional compounds can be chosen from alkanediols,alkanetriols, polyalkanediols, dihydroxy telechelics, and trihydroxytelechelics, such as those disclosed herein. Mechanisms of thecondensation/transesterification reactions can be:

where —(R₈)_(x)—NHR₂ and —(R₇)_(y)—COOR₉ are ortho, meta, or parasubstituents on the cyclic rings; A is the same or different moietieschosen from O, S, and NR, R being hydrogen or organic moieties havingabout 1-20 carbon atoms, such as 1-12 carbon atoms; R₁ is a divalent orpolyvalent organic moiety having at least one carbon or silicon atom,such as about 1,000 carbon or silicon atoms or less; R₂ is hydrogen ororganic moiety having 1 to about 20 carbon atoms, such as 1-6 carbonatoms; R₃ to R₆ are independently chosen from hydrogen, halides, nitro,and organic moieties having about 1-20 carbon atoms, such as about 1-6carbon atoms; R₇ is an organic moiety having at least one C, O, N, S, orSi atom, such as a divalent, linear or branched organic moiety havingabout 60 carbon atoms or less, or about 20 carbon atoms or less; R₈ is adivalent organic moiety having one carbon atom connecting NHR₂ to thecyclic ring, such as —CH₂—, —CH(CH₃)—, —CH(CH₂CH₃)—, or —C(CH₃)₂—; R₉ ischosen from hydrogen and organic moieties having about 1-20 carbonatoms, such as about 1-12 carbon atoms; m is at least 1, such as about2-10, like 2, 3, 4, and any numbers therebetween; x, y, and z areindependently 0 or 1. One or more of R, R₁ to R₆ and R₉ can have one ormore heteroatoms chosen from O, N, S, and Si.

R₁ can be linear or branched, divalent or trivalent, substituted (suchas halogenated) or unsubstituted, aliphatic, cyclic, alicyclic,aromatic, or araliphatic, include alkylene moieties having about 1-60,about 1-20, or about 1-12 carbon atoms, such as methylene, ethylene,propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene,decylene, undecylene, and dodecylene moieties. R₉ can be linear orbranched, substituted (such as halogenated) or unsubstituted, aliphatic,cyclic, alicyclic, aromatic, or araliphatic, include alkyl moieties suchas methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, anddodecyl.

Non-limiting examples of suitable aromatic amino acids and estersthereof include 2-aminobenzoic acid, 2-amino-(3, 4, 5, or6)-methylbenzoic acid, 5-nitro anthranilic acid, 2-amino-(3 or5)-hydroxybenzoic acid, 2-amino-(3, 4, 5, or 6)-chlorobenzoic acid,2-amino-6-bromo-5-methylbenzoic acid, 2-amino-phenylacetic acid,2-amino-3-benzoylphenylacetic acid,2-amino-3-(4-bromobenzoyl)phenylacetic acid, 3-aminobenzoic acid,3-amino-4-methylbenzoic acid, 3-amino-4-methoxybenzoic acid, 3-amino-(2,4, or 6)-chlorobenzoic acid, 3-amino-phenylacetic acid,methyl-2-aminobenzoate, methyl-2-amino-5-bromobenzoate,methyl-2-amino-3,5-dibromobenzoate, ethyl-2-aminobenzoate,pentyl-2-aminobenzoate, 2-propenyl-2-aminobenzoate,cyclohexyl-2-aminobenzoate, methyl-2-methylaminobenzoate,methyl-2-methylaminobenzoate, sec-butyl-2-methylaminobenzoate,methyl-3-aminobenzoate, methyl-3-amino-4-methylbenzoate,methyl-3-amino-4-methoxybenzoate, ethyl-3-aminobenzoate, and mixturesthereof. Illustrative examples of cyclohexane analogs to theaminobenzoic acids include, but are not limited to,2-aminomethyl-cyclohexane carboxylic acid and 3-aminomethyl-cyclohexanecarboxylic acid.

The sterically hindered polyamines can also be obtained by reacting theactive hydrogen functional compound or telechelic with a substituted orunsubstituted oxazine dione (e.g., anhydrides), such as a benzoxazinedione or cyclohexane oxazine dione having the generic structures of:

where R is chosen from hydrogen and organic moieties having about 1-20carbon atoms, such as about 1-6 carbon atoms; Z₁ to Z₄ are independentlychosen from hydrogen, halides, nitro groups, and organic moieties havingabout 1-20 carbon atoms, such as about 1-6 carbon atoms. One or more ofR and Z₁ to Z₄ may contain one or more heteroatoms such as O, N, S, orSi, and/or may be partially or fully halogenated. Non-limiting examplesinclude isatoic anhydride, N-methyl isatoic anhydride, 5-nitro-isatoicanhydride, 3-methyl-benzoxazine-2,4-dione,3-phenyl-1,3-benzoxazine-2,4-dione,3-(4-methylphenyl)-1,3-benzoxazine-2,4-dione,1-[3-(perfluorooctyl)propyl]-(1H-benzo[d][1,3]oxazine-2,4-dione(F-Isatoic Anhydride available from Fluorous Technologies, Inc. ofPittsburgh, Pa.), and mixtures thereof.

The various reaction themes described above for preparing stericallyhindered polyamines can be applied to other cyclic analogs where thebenzene or cyclohexane rings of the above-mentioned reactants andreaction products are replaced by other saturated or unsaturated4-membered or larger cyclic structures, including monocyclics,polycyclics (fused, spiro, and/or bridged), and heterocyclics, such ascyclopentane. In the case of saturated cyclic structures, the at leastone amine-containing substitution and the at least oneacid/ester-containing substitution may be directly attached to the samering-member carbon atom, as in the case of 1-aminocyclopentanecarboxylic acid.

The sterically hindered polyamines can further be prepared by reactingthe amino acids or esters mentioned above with diamines and polyaminesdisclosed herein, such as alkanediamines, alkanetriamines, and thevarious polyamine telechelics. In this case, the reaction forms two ormore amide linkages rather than ester linkages.

Polyol Telechelics

Any polyol telechelics available or known to one of ordinary skill inthe art are suitable for use in compositions of the disclosure. Polyoltelechelic such as α,ω-dihydroxy telechelics, include polyolpolyhydrocarbons (such as polyol polyolefins), polyol polyethers, polyolpolyesters (such as polyol polycaprolactones), polyol polyamides (suchas polyol polycaprolactams), polyol polycarbonates, polyol polyacrylates(such as polyol polyalkylacrylates), polyol polysiloxanes, polyolpolyimines, polyol polyimides, and polyol copolymers including polyolpolyolefinsiloxanes (such as α,ω-dihydroxypoly(butadiene-dimethylsiloxane) and α,ω-dihydroxypoly(isobutylene-dimethylsiloxane)), polyol polyetherolefins (such asα,ω-dihydroxy poly(butadiene-oxyethylene)), polyol polyetheresters,polyol polyethercarbonates, polyol polyetheramides, polyolpolyetheracrylates, polyol polyethersiloxanes, polyol polyesterolefins(such as α,ω-dihydroxy poly(butadiene-caprolactone) and α,ω-dihydroxypoly(isobutylene-caprolactone)), polyol polyesteramides, polyolpolyestercarbonates, polyol polyesteracrylates, polyolpolyestersiloxanes, polyol polyamideolefins, polyol polyamidecarbonates,polyol polyamideacrylates, polyol polyamidesiloxanes, polyolpolyamideimides, polyol polycarbonateolefins, polyolpolycarbonateacrylates, polyol polycarbonatesiloxanes, polyolpolyacrylateolefins (such as α,ω-dihydroxy poly(butadiene-methylmethacrylate), α,ω-dihydroxy poly(isobutylene-t-butyl methacrylate), andα,ω-dihydroxy poly(methyl methacrylate-butadiene-methyl methacrylate)),polyol polyacrylatesiloxanes, polyol polyetheresteramides, any otherpolyol copolymers, as well as blends thereof. Other polyol telechelicscan be derived from polyacid telechelics through reaction with polyols,aminoalcohols, and/or cyclic ethers, or derived from polyaminetelechelics through reaction with hydroxy acids, cyclic esters, and/orcyclic ethers as disclosed herein.

The molecular weight of the polyol telechelics can be about 100-20,000,such as about 200, about 230, about 500, about 600, about 1,000, about1,500, about 2,000, about 2,500, about 3,000, about 3,500, about 4,000,about 5,000, about 8,000, about 10,000, or any number therebetween. Thepolyol telechelics can have one or more hydrophobic and/or hydrophilicsegments.

a) Polyol Polyhydrocarbons

An example of polyol polyhydrocarbons has a generic structure of:

where R₃ to R₅ are independently chosen from linear, branched, cyclic(including monocyclic, aromatic, bridged cyclic, spiro cyclic, fusedpolycyclic, and ring assemblies), saturated, unsaturated, hydrogenated,and/or substituted hydrocarbon moieties having about 2-30 carbon atoms;x, y, and z are independently zero to about 200, and x+y+z≧2. R₃ to R₅can independently have the structure C_(n)H_(m), where n is an integerof about 2-30, and m is zero to about 60. Any one or more of thehydrogen atoms in R₃ to R₅ may be substituted with halogens, cationicgroups, anionic groups, silicon-based moieties, ester moieties, ethermoieties, amide moieties, urethane moieties, urea moieties,ethylenically unsaturated moieties, acetylenically unsaturated moieties,aromatic moieties, heterocyclic moieties, hydroxy groups, amine groups,cyano groups, nitro groups, and/or any other organic moieties. One ormore of R₃ to R₅ can have the structure C_(n)H_(2n), n being an integerof about 2-20, and x+y+z is about 5-100.

Polyol polyhydrocarbons are hydrophobic in general, and provide reducedmoisture absorption and permeability to the elastomer compositions ofthe present disclosure. Non-limiting examples of polyol polyhydrocarbonsinclude α,ω-dihydroxy polyolefins such as α,ω-dihydroxy polyethylenes,α,ω-dihydroxy polypropylenes, α,ω-dihydroxy polyethylenepropylenes,α,ω-dihydroxy polyisobutylenes, α,ω-dihydroxy polyethylenebutylenes(with butylene content of at least about 25% by weight, such as at leastabout 50%), hydroxyl-terminated Kraton rubbers; α,ω-dihydroxy polydienessuch as α,ω-dihydroxy polyisoprenes, partially or fully hydrogenatedα,ω-dihydroxy polyisoprenes, hydroxyl-terminated liquid isoprenerubbers, α,ω-dihydroxy polybutadienes, partially and/or fullyhydrogenated α,ω-dihydroxy polybutadienes; as well as α,ω-dihydroxypoly(olefin-diene)s such as α,ω-dihydroxy poly(styrene-butadiene)s,α,ω-dihydroxy poly(ethylene-butadiene)s, and α,ω-dihydroxypoly(butadiene-styrene-butadiene)s.

The polyol polyhydrocarbons can be polyol polydienes, which also includepolyol poly(alkylene-diene)s, as well as blend thereof. Polyolpolydienes can have M_(n) of about 1,000-20,000, such as about1,000-10,000 or about 3,000-6,000, and a hydroxyl functionality of about1.6-10, such as about 1.8-6 or about 1.8-2. The diene monomers can beconjugated dienes, such as 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, and mixtures thereof. The polyol polydienecan be substantially hydrogenated to improve stability, such that atleast about 90%, or at least about 95%, of the carbon-carbon doublebonds in the polyol are hydrogenated.

Unhydrogenated, partially hydrogenated, and fully hydrogenated polydienediols and copolydiene diols, among other polyol telechelics, are capableof imparting high resiliency in the compositions. The polydiene diol canbe polybutadiene diol having 1,4-addition of about 30-70%, such as about40-60%. The polybutadiene diol can have 1,2-addition of at least about40%, such as about 40-60%, so that the hydrogenated polybutadiene diolremains liquid at ambient temperature. The polybutadiene diol can bemore than about 99% hydrogenated, having M_(n) of about 3,300, ahydroxyl functionality of about 1.92, and a 1,2-addition content ofabout 54%. The polydiene diol can be a polyisoprene diol having1,4-addition of at least about 80% to reduce glass transitiontemperature and viscosity.

One group of copolydiene diols has a generic structure of:

where R₃ is chosen from hydrogen, linear and branched alkyl groups (suchas methyl), cyano group, phenyl group, halide, and mixture thereof; R₄is chosen from hydrogen, linear and branched alkyl group (such asmethyl), halide (such as chloride or fluoride), and mixture thereof; xand y are independently about 1-200. The y:x ratio can be about 82:18 toabout 90:10. The copolydiene diol can be substantially hydrogenated(i.e., substantially all of the >C══CH— or >C══CH₂ moieties arehydrogenated into >CH—CH₂— or >C—CH₃ moieties, respectively). Oneexample is hydrogenated poly(acrylonitrile-co-butadiene) diol, where R₃is cyano group, and R₄ is hydrogen.

b) Polyol Polyethers

An example of the polyol polyethers has a generic structure of:

where R₃ to R₆ are independently chosen from linear, branched, or cyclicmoieties having at least one carbon atom, such as about 60 carbon atomsor less; i is about 2-10, such as about 2-6; x is about 1-200, and y andz are independently zero to about 200. Any one or more of the hydrogenatoms in R₃ to R₆ may be substituted with halogens, cationic groups,anionic groups, silicon-based moieties, ester groups, ether groups,amide groups, urethane groups, urea groups, ethylenically unsaturatedgroups, acetylenically unsaturated groups, amine groups, hydroxylgroups, or any other organic moieties. R₃ to R₆ can independently havethe structure C_(n)H_(m), where n is an integer of about 1-30, and m isan integer of about 2-60. R₃ and R₅ can be identical. The number x canbe about 2-70, such as about 5-50 or about 12-35. Alternatively, y+z isabout 2-10, while x is about 8-50.

Commercial examples of polyol polyethers include, but are not limitedto, polyoxyethylene diols, polyoxypropylene diols,α,ω-bis(2-hydroxypropyl)polyoxypropylenes (such as having M_(w) of about200-5,000), polyoxytetramethylene diols (i.e., polytetrahydrofurans,such as having M_(w) of about 200-2,000), modified polyoxytetramethylenediols, poly(oxyethylene-oxypropylene) diols,α,ω-bis(3-hydroxypropyl)poly(oxyethylene-capped oxypropylene),poly(oxybutylene-oxypropylene-oxyethylene) diols, polyoxyalkylene diolsinitiated by bisphenol A or primary monools, tri-block polyol polyetherssuch as poly(oxypropylene-block-oxyethylene-block-oxypropylene) diolsand poly(oxyethylene-block-oxypropylene-block-oxyethylene) diols,polyoxypropylene triols initiated by glycerin, trimethylolethane, ortrimethylolpropane, polyoxypropylene tetraols initiated bypentaerythritol, ethylenediol, phenolic resin, or methyl glucoside,diethylenetriol-initiated polyoxypropylene pentaols, sorbitol-initiatedpolyoxypropylene hexaols, and sucrose-initiated polyoxypropyleneoctaols. Other suitable polyether polyols include those described inco-owned and co-pending application bearing Ser. No. 10/434,739, thedisclosure of which is incorporated herein by reference in its entirety.

R₃ and R₅ can be the same linear, branched, or cyclic radicals having atleast about 10 carbon atoms, such as at least about 18 carbon atoms, orat least about 30 carbon atoms, and y and z are both zero. The polyolpolyether of the structure (57) thus becomes HO—[R₃—O]_(x)—R₃—OH. R₃ canbe an alkylene moiety, while x is about 1-50, such as about 1.5-30. Thepolyether backbone can be prepared by acid-catalyzed polycondensation ofsuitable low molecular weight alkylene glycols such as dimer diols atelevated temperature (e.g., 150-250° C.). These polyol polyethers can behydrophobic. When x is less than about 10, such as about 1.5-7, likeabout 2, about 4, or about 5, these polyol polyethers can be liquid atambient temperature, having a viscosity at 25° C. of about 3,000-12,000cP. The hydrophobicity of such polyether polyols can enhance hydrolysisresistance of the compositions and reduce moisture absorption. These andother polyol telechelics as described in U.S. Pat. No. 5,616,679 areincorporated herein by reference.

In the structure of (57), R₅ and R₆ can be identical, R₄ and R₅ can bethe same or different alkylene groups having about 2-40 carbon atoms,such as about 2-20, about 2-10, or about 2-4 carbon atoms, R₃ can be thebackbone of a dimer diol as disclosed herein below, x can be 1, and40≧(y+z)≧1. As such, the structure (57) becomesHO—[R₄—O]_(y)—R₃—[O—R₅]_(z+1)—OH. These polyol polyethers arehydrolysis-resistant, and typically have M_(w) of about 600-3,000. Thepolyether backbone can be produced by adding cyclic ethers (i.e.,alkylene oxides such as ethylene oxide, propylene oxide, butylenesoxide, tetrahydrofuran, methyl tetrahydrofuran, and mixtures thereof)onto a dimer diol. Other suitable cyclic ethers include the chiralcyclic ethers described in co-owned and co-pending application bearingthe Ser. No. 10/434,739, which is incorporated by reference herein.

A blend of two polyol polyethers can be used to form the prepolymer,wherein the first polyol polyether has a first molecular weight of about3,500-6,500, a first hydroxyl functionality of about 3 or less, and afirst oxyethylene content of about 8-20% by weight, while the secondpolyol polyether has a second molecular weight of about 4,000-7,000, asecond hydroxyl functionality of about 4-8, and a second oxyethylenecontent of about 5-15% by weight. The first polyol polyether canconstitute about 70-98% by weight of the blend, and the second polyolpolyether can constitute about 2-30% by weight of the blend. A mixturehaving about 25-95% by weight of this polyol polyether blend and about5-75% by weight of at least a third polyol telechelic different from thefirst and second polyether polyols is also suitable to formulate aresilient elastomer composition.

In one example, the polyol telechelic comprises a polyether triol havingM_(w) of about 4,500-6,000 and an average hydroxyl functionality ofabout 2.4-3.5, such as about 2.4-2.7. In another example, the polyolpolyether has a weight average unsaturation of about 0.03 meq/g or less,as measured by ASTM D-2849-69, such as about 0.02 meq/g or less, about0.015 meq/g or less, even about 0.01 meq/g or less, and M_(w) of about1,500-5,000. In a further example, the polyol polyether comprises atleast one random poly(oxyethylene-oxyalkylene) terminal block orpolyoxyethylene terminal block, having oxyethylene moieties in theamount of about 12-30% by weight of the polyol polyether. Low level ofaverage unsaturation of about 0.002-0.007 meq/g is achieved in thepolyol polyether by using double metal cyanide catalysts when formingthe polyether backbone. The polyol polyethers can also have a lowpolydispersity of about 1.2 or less.

The polyol polyether can have repeating branched oxyalkylene monomerunits derived from branched diol monomers, chiral diol monomers,alkylated cyclic ethers, and/or chiral cyclic ethers, throughhomo-polymerization, co-polymerization, and/or ring-openingpolymerization, optionally in combination with a second diol or cyclicether. As a non-limiting illustration, the chiral diol may be2-methyl-1,4-butanediol; the chiral cyclic ether may be2-methyl-tetrahydrofuran; the second diol may be 1,4-butanediol(achiral); and the second cyclic ether may be tetrahydrofuran (achiral).Other chiral diols include 2,4-petanediol and 3-methyl-1,3-butanediol.Exemplary linear and branched oxyalkylene monomer units include, but arenot limited to, —O—CH₂—CH(CH₃)—(CH₂)₂—, —O—(CH₂)₃—, —O—(CH₂)₂—,—O—C(CH₃)₂—CH₂—, —O—(CH₂)₂—CH(CH₃)—CH₂—, —O—CH₂—CH(CH₃)—,—O—CH(CH₂CH₃)—CH₂—, —O—CH₂—CH(CH₃)—CH₂—, —O—(CH₂)₃—CH(CH₃)—,—O—CH₂—C(CH₃)₂—, —O—CH(CH₃)—CH₂—, —O—(CH₂)₅—, —O—CH₂—CH(CH₂CH₃)—,—O—CH(CH₃)—(CH₂)₃—, —O—(CH₂)₄—, —O—CH(CH₃)—(CH₂)₂—, and—O—(CH₂)₂—CH(CH₃). The polyol polyether can be obtained bycopolymerizing chiral diol/ether and achiral diol/ether at a molar ratioof about 85:15 to about 20:80. A non-limiting example of such polyetherpolyols is referred to as a modified PTMEG diol, or an α,ω-dihydroxypoly(tetrahydrofuran-co-methyltetrahydrofuran) ether.

c) Polyol Polyesters

An example of the polyol polyesters has a generic structure of:

where R₃ to R₉ are independently chosen from linear, branched, andcyclic moieties having 1 to about 60 carbon atoms; Z is the same ordifferent moieties chosen from —O— and —NH—; i is about 2-10, such asabout 2-6; x is about 1-200, and y and z are independently zero to about200. The number x can be the same or different numbers. R₃ to R₉ canindependently have the structure C_(n)H_(m), where n is an integer ofabout 2-30, and m is an integer of about 2-60. Any one or more of thehydrogen atoms in R₃ to R₉ may be substituted with halogens, cationicgroups, anionic groups, silicon-based moieties, ester groups, ethergroups, amide groups, urethane groups, urea groups, ethylenicallyunsaturated groups, acetylenically unsaturated groups, amine groups,hydroxyl groups, or any other organic moieties. R₃ and R₆ can beidentical, having a structure C_(n)H_(2n), n being an integer of about2-30, x+y+z is about 1-100, such as about 5-50.

The polyol polyester can have a crystallization enthalpy of at mostabout 70 J/g and M_(n) of about 1,000-7,000, such as about 1,000-5,000.This polyol polyester can be blended with a polyol polyether havingM_(n) of about 500-2,500. The average hydroxyl functionality of theblend, which is the ratio of total number of hydroxyl groups in theblend to total number of telechelic molecules in the blend, can be about2-2.1. The polyol polyester can have an ester content (number of esterbonds/number of all carbon atoms) of about 0.2 or less, such as about0.08-0.17.

The polyester chain can be formed from condensation polymerizationreaction of polyacids and/or anhydrides with excess polyols.Alternatively, the polyester chain can be formed at least in part fromring-opening polymerization of cyclic esters. The polyester chain canalso be formed at least in part from polymerization of hydroxy acids,including those that structurally correspond to the cyclic esters.Obviously, the polyester chain can comprise multiple segments formedfrom polyacids, anhydrides, polyols, cyclic esters, and/or hydroxyacids, non-limiting examples of which are disclosed herein. Suitablereactants also include polyacid telechelics, polyol telechelics, andhydroxy acid polymers. In one example, at least one polyacid, anhydride,polyol, cyclic ester, or hydroxy acids having M_(n) of at least about200, such as at least about 400, or at least about 1,000, is used toform the polyester chain. In another example, the polyester chain has 1to about 100 ester linkages, such as about 2-50, or about 2-20.

The polyol polyesters can be formed from the condensation of one or morepolyols having about 2-18 carbon atoms, such as about 2-6 carbon atoms,with one or more polycarboxylic acids or their anhydrides having fromabout 2-14 carbon atoms. Non-limiting examples of polyols includeethylene glycol, propylene glycol such as 1,2-propylene glycol and1,3-propylene glycol, glycerol, pentaerythritol, trimethylolpropane,1,4,6-octanetriol, butanediol, pentanediol, hexanediol, dodecanediol,octanediol, chloropentanediol, glycerol monoallyl ether, glycerolmonoethyl ether, diethylene glycol, 2-ethylhexanediol-1,4,cyclohexanediol-1,4,1,2,6-hexanetriol, neopental glycol,1,3,5-hexanetriol, 1,3-bis-(2-hydroxyethoxy)propane and the like. Cyclicethers having about 2-18 carbon atoms may be used in place of or inaddition to the polyols. Non-limiting examples of polycarboxylic acidsinclude phthalic acid, isophthalic acid, terephthalic acid,tetrachlorophthalic acid, maleic acid, dodecylmaleic acid,octadecenylmaleic acid, fumaric acid, aconitic acid, trimellitic acid,tricarballylic acid, 3,3′-thiodipropionic acid, succinic acid, adipicacid, malonic acid, glutaric acid, pimelic acid, sebacic acid,cyclohexane-1,2-dicarboxylic acid, 1,4-cyclohexadiene-1,2-dicarboxylicacid, 3-methyl-3,5-cyclohexadiene-1,2-dicarboxylic acid and thecorresponding acid anhydrides, acid chlorides and acid esters such asphthalic anhydride, phthaloyl chloride and the dimethyl ester ofphthalic acid.

Examples of polyol polyesters include, without limitation, poly(ethyleneadipate) diols, poly(butylene adipate) diols, poly(1,4-butyleneglutarate) diols, poly(ethylene propylene adipate) diols, poly(ethylenebutylene adipate) diols, poly(hexamethylene adipate) diols,poly(hexamethylene butylene adipate) diols, poly(hexamethylenephthalate) diols, poly(hexamethylene terephthalate) diols,poly(2-methyl-1,3-propylene adipate) diols, poly(2-methyl-1,3-propyleneglutarate) diols, and poly(2-ethyl-1,3-hexylene sebacate) diols.Non-limiting examples of polyester polyols based on fatty polyacids orpolyacid adducts, such as those disclosed herein, include poly(dimeracid-co-ethylene glycol) hydrogenated diols and poly(dimeracid-co-1,6-hexanediol-co-adipic acid) hydrogenated diols.

An example of the polyol polycaprolactones has a generic structure of:

where R₃, Z, i, x are as described above. The number x can the same ordifferent, and can be about 5-100. Suitable polycaprolactone polyolsinclude, but are not limited to, polyol-initiated andpolyamine-initiated ring-opening polymerization products ofcaprolactone, and polymerization products of hydroxy caproic acid.Suitable polyol and polyamine initiators include any polyols andpolyamines available to one of ordinary skill in the art, such as thosedisclosed herein, as well as any and all of the polyol telechelics andpolyamine telechelics of the present disclosure. The caprolactonemonomer can be replaced by or blended with any other cyclic estersand/or cyclic amides as disclosed herein.

Polyamine-initiated and polyol-initiated polycaprolactone polyolsinclude, but are not limited to, bis(2-hydroxyethyl) ether initiatedpolycaprolactone polyols, 2-(2-aminoethylamino) ethanol initiatedpolycaprolactone polyols, polyoxyethylene diol initiatedpolycaprolactone polyols, propylene diol initiated polycaprolactonepolyols, polyoxypropylene diol initiated polycaprolactone polyols,1,4-butanediol initiated polycaprolactone polyols,trimethylolpropane-initiated polycaprolactone polyols,hexanediol-initiated polycaprolactone polyols, polytetramethylene etherdiol initiated polycaprolactone polyols, bis(2-aminoethyl)amineinitiated polycaprolactone polyols, 2-(2-aminoethylamino) ethylamineinitiated polycaprolactone polyols, polyoxyethylene diamine initiatedpolycaprolactone polyols, propylene diamine initiated polycaprolactonepolyols, polyoxypropylene diamine initiated polycaprolactone polyols,1,4-butanediamine initiated polycaprolactone polyols, neopentyl diamineinitiated polycaprolactone polyols, hexanediamine-initiatedpolycaprolactone polyols, polytetramethylene ether diamine initiatedpolycaprolactone polyols, and mixtures thereof.

d) Polyol Polyamides

An example of the polyol polyamides has a generic structure of:

where R₁ and R₂ are independently chosen from aliphatic, alicyclic,araliphatic, and aromatic moieties; R₃ to R₉ are independently chosenfrom linear, branched, and cyclic moieties having 1 to about 60 carbonatoms; Z is the same or different moieties chosen from —O— and —NH—; iis about 2-10, such as about 2-6; x is the same or different numbers ofabout 1-200, and y and z are independently zero to about 200. R₃ can bea polymeric chain such as those disclosed herein. The number x can bethe same or different numbers, and y is 1 or greater but less than x. R₃to R₉ can independently have the structure C_(n)H_(m), where n is aninteger of about 2-30, and m is an integer of about 2-60. Any one ormore of the hydrogen atoms in R₁ to R₉ may be substituted with halogens,cationic groups, anionic groups, silicon-based moieties, ester groups,ether groups, amide groups, urethane groups, urea groups, ethylenicallyunsaturated groups, acetylenically unsaturated groups, amine groups,hydroxyl groups, or any other organic moieties. R₁ and R₂ can beidentical. R₃ and R₆ can be identical, having a structure ofC_(n)H_(2n), n being an integer of about 2-30, x+y+z is about 1-100,such as about 5-50. Polyol polyamides can be linear, branched,star-shaped, hyper-branched or dendritic.

Polyol polyamides of the structures (64), (66), and (67) can be formedby reacting the corresponding polyamine polyamides as described abovewith cyclic esters and/or hydroxy acids such as those disclosed herein.Using this reaction scheme, any and all of polyamine telechelics andpolyamines such as those disclosed herein can be converted to polyoltelechelics and/or polyols through the formation of two or more amidelinkages, wherein with respect to a center point of the polyoltelechelic, the nitrogen atom is of closer proximity than the carbonatom in each of these amide linkages. The reaction product can alsocontain polyol telechelics having terminal polyester block segmentsfollowing the amide linkages. Polyol polyamides of the structures (65)and (68) can be formed by reacting polyacid polyamides (i.e., polyacidtelechelics formed such as from polyamines and excess polyacids, with anequivalent ratio of polyamine to polyacid being less than 1, such asabout 0.2-0.9) with any of the aminoalcohols or polyol amines disclosedherein. Using this reaction scheme, any and all polyacid telechelics andpolyacids such as those disclose herein can be converted to polyoltelechelics and/or polyols through the formation of two or more amidelinkages, wherein with respect to a center point of the polyoltelechelic, the carbon atom is of closer proximity than the nitrogenatom in each of these amide linkages.

An example of the polyol polycaprolactam has a generic structure of:

where R₃ to R₅, Z, i, x are as described above. The number x can be thesame or different, and can be about 5-100. R₄ and R₅ can be identical,and can both be (CH₂)₅. Suitable polycaprolactam polyols include, butare not limited to, those having polyamide backbones and/or chainsformed from polyol-initiated and/or polyamine-initiated ring-openingpolymerization of caprolactam, and polymerization products of aminocaproic acid.

e) Polyol Polycarbonates

An example of the polyol polycarbonates has a generic structure of:

where R₃ to R₆ are independently chosen from linear, branched, cyclic,aliphatic, alicyclic, araliphatic, aromatic, and ether moieties having 1to about 60 carbon atoms; x is about 1-200, and y and z areindependently zero to about 200. R₃ to R₆ can independently have thestructure C_(n)H_(m), where n is an integer of about 2-30, and m is aninteger of about 2-60. Any one or more of the hydrogen atoms in R₃ to R₆may be substituted with halogens, cationic groups, anionic groups,silicon-based moieties, ester groups, ether groups, amide groups,urethane groups, urea groups, ethylenically unsaturated groups,acetylenically unsaturated groups, amine groups, hydroxyl groups, or anyother organic moieties. R₃ and R₆ can be identical. R₃, R₅ and R₆ canall be identical. The polyol polycarbonate can be substantially free ofether linkages.

When y and z are both zero, the polyol polycarbonate can besubstantially crystalline. Examples include poly(phthalate carbonate)glycols, poly(hexamethylene carbonate) glycols, and polycarbonateglycols comprising Bisphenol A. When at least one of y and z is greaterthan zero, and at least one of R₄ and R₅ is different from R₃, thepolyol polycarbonate becomes amorphous due to reduction in cohesiveenergy density, and displays lowered crystallinity, lowered hysteresis,and improved impact resistance as compared to crystalline polyolpolycarbonates. Non-limiting examples of R₃ to R₆ include —(CH₂)_(n)—where n is about 1-16, such as hexamethylene (n=6); —CH₂C₆H₁₀CH₂—(1,4-cyclohexane dimethylene); —C₆H₅C(CH₃)₂C₆H₅— (bisphenol A); and—(C_(m)H_(2m)O)_(n)C_(m)H_(2m)— where m is about 1-6, and n is about1-16, such as trioxyethylene (m is 2, n is 2). A non-limiting example ofsuch amorphous polyol copolycarbonates is poly(hexamethylenecarbonate-block-trioxyethylene carbonate-block-hexamethylene carbonate)diol. Other suitable polyol polycarbonates are described in U.S. Pat.Nos. 6,197,051, 6,177,522, 5,863,627, 5,859,122, 5,621,065, and5,001,208, as well as in co-owned and co-pending U.S. Patent ApplicationNo. 20030078341, bearing Ser. No. 10/277,153. The disclosures thesepatents and applications are incorporated herein by reference in theirentirety. In one example, the polyol polycarbonate can have at least onesegment based exclusively or predominantly on 1,6-hexanediol, incombination with diaryl carbonate, dialkyl carbonate, dioxolanone,phosgene, bis-chlorocarbonate, and/or urea.

Other polyol polycarbonates can have the following structure:

where R₃ is chosen from linear, branched, cyclic, aliphatic, alicyclic,araliphatic, and aromatic moieties having about 4-40 carbon atoms, andalkoxy moieties having about 2-20 carbon atoms; R₄ is chosen fromlinear, branched, cyclic, aliphatic, alicyclic, araliphatic, andaromatic moieties having about 2-20 carbon atoms, and organic moietieshaving about 2-4 linear carbon atoms in the main chain with or withoutone or more pendant carbon groups; x is the same or different numbers ofabout 2-50, such as about 2-35; and y is the same or different numberschosen from 0, 1, and 2.

The polycarbonate chain can be produced by a number of differentmethods. With interfacial polymerization, polycarbonate chain can bemade from polyols such as bisphenols (e.g., phosgene) in a two-phasereaction (i.e., water and immiscible organic solvent) with a phasetransfer catalyst. Polycarbonate chain can also be made bytransesterification between a polyol (or a blend of two or moredifferent polyols, like 1,6-hexanediol) and a carbonate (aliphaticcarbonate such as alkyl carbonate or alkylene carbonate, or aromaticcarbonate, or a blend thereof, like ethylene carbonate), such as adiester of carbonic acid having a structure of R′O(CO)OR″, where R′ andR″ can be independently chosen from alkyl, aryl, aralkyl, alicyclic,cycloalkyl, and other organic moieties having about 1-20 carbon atoms(such as dialkyl carbonate and diphenyl carbonate). Polycarbonatebackbone may further be synthesized from CO₂ and epoxide (such ascyclohexene oxide and propylene oxide) or oxetane, with the help of acatalyst. Alternatively, the polycarbonate backbone can be acondensation product of CO₂, dihalide, and dialkoxide or a combinationof K₂CO₃ and polyol (such as diol). Polycarbonate diols can besynthesized using one or a blend of two or more cyclic diols. Othermethods for producing the polycarbonate backbone include chloroformateprocess. Obviously, the polycarbonate backbone can comprise multiplesegments formed from different polyols and carbonates. Suitable polyolscan be any and all polyols disclosed herein, including the variouspolyol telechelics. Suitable carbonates include any and all carbonatesavailable to one skilled in the art, such as linear, branched, cyclic,aliphatic, alicyclic, and/or saturated carbonates. In one example, atleast one polyol or carbonate having M_(w) of at least about 200, suchas at least about 400 or at least about 1,000 is used to form thebackbone.

f) Polyol Polyimines

Polyol polyimines include polyimines grafted with polymeric segmentssuch as, without limitation, polyethylene glycol and methoxylatedpolyethylene glycol, and hyper-branched and dendritic macromolecules(e.g., dendrimers and tecto-dendrimers), such as those described inco-owned and co-pending U.S. patent application Ser. No. 10/456,295.Dendrimers may have hydroxyl, amidoethanol, and/or amidoethylethanololas surface end-groups. Alternatively, polyol polyimines can be preparedfrom polyamine polyimines by reacting with cyclic esters, such as thosedisclosed herein.

g) Polyol Polyacrylates

An example of polyol polyacrylates has a generic structure of:

where R₃ to R₈ are independently chosen from hydrogen, aliphatic,alicyclic, aromatic, carbocyclic, heterocyclic, halogenated, andsubstituted moieties, each having about 20 carbon atoms or less; X and Yare optional, independently chosen from alkyl, aryl, mercaptoalkyl,ether, ester, carbonate, acrylate, halogenated, and substitutedmoieties; x is about 1-200, and y and z are independently zero to about100. R₃ to R₈ can independently have the structure C_(n)H_(m), where nis an integer of about 2-20, and m can be an integer of about 2-40. Anyone or more of the hydrogen atoms in R₃ to R₈ may be substituted withhalogens, cationic groups, anionic groups, silicon-based moieties, estergroups, ether groups, amide groups, urethane groups, urea groups,ethylenically unsaturated groups, acetylenically unsaturated groups,amine groups, hydroxyl groups, or any other organic moieties. R₄, R₆,and R₈ can independently be hydrogen or methyl group, while R₃, R₅, andR₇ can independently have a structure of C_(n)H_(2n), n being an integerof about 2-16, x+y+z being about 1-100, such as about 5-50.

Suitable polyol polyalkylacrylates include, but are not limited to,those disclosed in the co-pending application bearing Ser. No.10/640,532, which is incorporated herein by reference in its entirety.Non-limiting examples include α,ω-dihydroxy polymethylmethacrylates,α,ω-dihydroxy polybutylmethacrylates, and α,ω-dihydroxypolyethylhexylmethacrylates.

h) Polyol Polysiloxanes

An example of polyol polysiloxanes has a generic structure of:

where R₃ to R₈ are independently chosen from hydrogen, aliphatic,alicyclic, aromatic, carbocyclic, heterocyclic, halogenated, andsubstituted moieties, such as alkyl or phenyl moieties, each havingabout 20 carbon atoms or less; X and Y are optional, independentlychosen from alkyl, aryl, mercaptoalkyl, ether, ester, carbonate,acrylate, halogenated, and substituted moieties; m is about 1-200; n iszero to about 100; z is about 1-100. R₃ to R₈ can independently have thestructure C_(n)H_(m), where n is an integer of about 2-20, and m is aninteger of about 2-40. Any one or more of the hydrogen atoms in R₃ to R₈may be substituted with halogens, cationic groups, anionic groups,silicon-based moieties, ester groups, ether groups, amide groups,urethane groups, urea groups, ethylenically unsaturated groups,acetylenically unsaturated groups, hydroxy groups, hydroxyl groups, orany other organic moieties. In one example, R₃═R₄, R₅═R₆, and R₇═R₈.

Suitable polysiloxane polyols include, but are not limited to, thosedisclosed in the co-pending application bearing Ser. No. 10/407,641,which is incorporated herein by reference in its entirety. Non-limitingexamples include bis(hydroxyalkyl) polydimethylsiloxanes,poly(dimethylsiloxane-co-diphenylsiloxane) diols,poly(dimethylsiloxane-co-methylhydrosiloxane) diols, andpolydimethylsiloxane diols. Non-limiting examples of polyolcopolysiloxanes include polysiloxaneether polyols obtained bycopolymerizing polysiloxane diol and polyether diol and/or cyclic ether,such as poly(dimethylsiloxane-oxyethylene) diols (i.e., ethoxylatedpolydimethylsiloxane diols), and polysiloxaneester polyols orpolysiloxaneamide polyols obtained by reacting polysiloxane diol withhydroxy acid or cyclic amide, respectively.

i) Fatty Polyol Telechelics

Fatty polyol telechelics include hydrocarbon polyol telechelics, adductpolyol telechelics, and various oleochemical polyol telechelics.Hydrocarbon polyol telechelics can have an all-carbon backbone of about8-100 carbon atoms, such as about 10, about 12, about 18, about 20,about 25, about 30, about 36, about 44, about 54, about 60, and anynumbers therebetween. Oleochemical polyol telechelics are often derivedfrom natural fats and oils which, if not having hydroxyl groups already,can have double bonds and/or carboxyl groups that may be converted intohydroxyl groups. Double bonds on fatty acids can be epoxidized byhydrogen peroxide to form multiple oxirane functionalities. Theseepoxidized fats and oils can be liquid at ambient temperature, and canbe used as phthalate-free, non-volatile, extraction and migrationresistant plasticizers/stabilizers, as polymer building blocks fornon-urethane compositions (e.g., linoleum, synthetic leather), or ascrosslinking agents for hydroxyl- and/or carboxyl-terminated polymers(e.g., polyesters, polyurethane, polyacrylate resins). They can bereacted with low molecular weight mono- and/or polyfunctional alcohols,acids, and/or or hydroxy acids to form ether polyols and/or esterpolyols, which may or may not contain oxirane groups (i.e., throughincomplete or complete reactions, respectively). Fatty polyoltelechelics derived as such can be liquid, of relatively low molecularweight, and may have reactive hydroxyl groups in the ester positionsonly (i.e., fatty acid polyol esters like glycerol monostearate), in thehydrocarbon chain only (i.e., fatty acid polyol esters of monofunctionalalcohols), or both (i.e., fatty acid polyol esters such as ricinoleicacid monoglyceride). These fatty polyol telechelics can be free oftriglyceride ester linkages.

One form of adduct polyol telechelics can be dimer diols, which can bealiphatic α,ω-diols having relatively high molecular weight. Dimer diolscan be produced by polymerization (e.g., dimerization) of one or moremonounsaturated and/or polyunsaturated fatty monoalcohols, such aspalmitoleyl, oleyl, elaidyl, linolyl, linolenyl and/or erucyl alcohols.The resulting dimer diols can be mixtures having a major content (e.g.,greater than about 50% by weight of the mixture) of dimer diols andrelatively minor contents (e.g., less than about 30%) of the monomeralcohols, trimers, and/or higher oligomers.

Dimer diols can also be prepared from dimer diacids and/or estersthereof, including dimethylesters and hydroxy acid methylesters, such asthose disclosed herein, by means of hydrogenation or condensation withpolyols (e.g., ethylene glycols) and/or polyacids (e.g., azelaic acids).The former can yield hydrocarbon polyol telechelics, whereas the latercan yield polyol polyesters. Starting from a distilled dimer diacid,hydrogenation can produce dimer diols having a dimer content of greaterthan about 90%, such as greater than about 95% by weight. The resultingdimer diols may be unsaturated, partly hydrogenated, or completelyhydrogenated (i.e., fully saturated). Likewise, castor oil can produce,through hydrolysis, esterification or transesterification, andhydrogenation, 12-hydroxystearyl alcohol having one primary and onesecondary hydroxyl group and a relatively high molecular weight.

Non-limiting dimer diols can have one of the following structures:

where x+y and m+n are both at least about 8, such as at least about 10,such as 12, 14, 15, 16, 18, 19, or greater.

Molecular weight of fatty polyol telechelics can be about 200-15,000,such as about 250-12,000, or about 500-5,000. Fatty polyol telechelicscan be liquid at room temperature, having low to moderate viscosity at25° C. (e.g., about 100-10,000 cP or about 500-5,000 cP). It ispostulated that highly branched polyols in general has desirableresistance to hydrolysis. As such, the fatty polyol telechelics can bebranched, such as with alkyl groups, thereby displaying improvedchemical stability, improved color stability (i.e., reduced yellowingbecause of reduction or elimination of unsaturation), high mechanicalstrength and durability, suitable in forming soft segments, and informulating solvent-free two pack full solid polyurethane/polyureacompositions. Because of their fluidity, these fatty polyol telechelicscan be used as reactive diluents in solvent-borne polyurethane/polyureacompositions to achieve higher solid content. Conventional volatilesolvents such as xylene, butyl acetate, methoxy propylacetate, ethoxypropylacetate may still be necessary to improve compatibility of resinand polyisocyanate, avoid phase separation, and adjust viscosity, butthe level of these non-reactive diluents can be significantly reduced.

j) Acid-Catalyzed Polyol Telechelics

Polyols and/or polyol telechelics of the present disclosure can bepolymerized into new polyol telechelics through, for example, acidcatalyzed dehydration. The condensation reaction can take place atelevated temperatures of at least about 150° C., and up to about200-250° C., and under normal pressure. The acid catalysts include, butare not limited to, sulfuric acid, hydrochloric acid, methane sulfonicacid, methane disulfonic acid, butane sulfonic acid, perfluorobutanesulfonic acid, benzene sulfonic acid, benzene disulfonic acid, toluenesulfonic acid, naphthalene disulfonic acid, methionic acid, phosphoricacid, perchloric acid, boron trifluoride, zinc chloride, quinolinehydrochloride, alkali metal hydrogen sulfates, other organic sulfonicacids, other aromatic sulfonic acids, other acidic salts, other readilyhydrolysable salts, other dissociating salts, acidic ion exchangerscontaining sulfonic acid group, and acidic aluminas. These catalysts canbe used individually or in combination of two or more thereof, in aquantity of about 0.1-30%, such as about 0.2-2% or about 0.5-15%, byweight of the starting polyols and/or polyol telechelics. Thecondensation reaction takes about 2-20 hours, such as about 6-12 hours,until the theoretically calculated quantity of water is obtained in thewater separator. The catalysts are hydrolyzed and precipitated out withaqueous alkali or ammonia. Solvents, unreacted starting materials,by-products such as ring ethers, and water are removed by azeotropicdistillation, evaporation in vacuo, and/or other conventional means. Thereaction product can be purified through distillation or fractionaldistillation.

The starting polyols and/or polyol telechelics include, but are notlimited to, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol,1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, dimerdiols, and other aliphatic diols. In one example, one of these diols byweight of at least about 50% can be blended with one or more of theother diols as the starting material. The reaction product can have astructure of HO—[R—O—]_(n)H, where R is a linear or branched alkyleneradical having about 5 carbon atoms or more, such as about 8, about 10,about 12, about 16, about 18, about 20, about 30, about 36, about 44,and about 54 carbon atoms or more; and n is more than 1, such as about 2or more. The main chain of R can have at least about 5 carbon atoms,such as about 8 or about 10 carbon atoms or more. The terminal hydroxylgroups can be primary. For molecularly non-uniform polyol polyethers,the number n can be about 0.5-5, such as 1.5-5. For molecularly uniformpolyol polyethers, the number n can be about 2-10, such as about 4-7.The reaction product can have a hydroxyl number of less than 750, suchas about 600, about 450, about 250, or about 175 or less, or about10-100, or any number therebetween. The reaction product can have anacid value of less than 5, such as about 1-3. The hydroxyl number is themilligrams of KOH equivalent to the quantity of acetic acid bound by 1 gof the reaction product during an acetylation reaction. The reactionproduct is boiled with acetic anhydride/pyridine and the acid formed isfiltered with KOH solution. The acid value is a measure of the contentof free organic acids in the reaction product. It indicates the numberof milligrams of KOH used to neutralized 1 g of the reaction product.The reaction product can have a viscosity at 25° C. of about 3,000 cP orgreater, such as about 3,800-12,000 cP, and a solubility in 100 ml ofwater at 20° C. of about 1 mg or less, such as about 0.1 mg or less.

k) Carbonate-Transesterified Polyol Telechelics

Polyol telechelics of the present disclosure, such as polyolpolyhydrocarbons, polyol polyethers, fatty polyol telechelics (such asdimer diols), and/or acid-catalyzed polyol telechelics as describedabove can be randomly copolymerized into new polyol telechelics throughtransesterification with carbonate-forming compounds at temperatures ofabout 120-220° C., such as about 130-200° C., under pressures of about0.1-200 mbar, such as about 0.1-100 mbar, over a period of about 6-20hours. The reaction may be catalyzed by bases or transition metalcompounds. By-products of the reaction can be moved via distillation.

The starting polyol telechelic can have a relatively low molecularweight, such as 150, 180, 300, 400, 5,00, 700, 800, 1,000, and anynumber therebetween. The starting polyol telechelic can be of a singlemolecular species, or a blend of two or more suitable polyoltelechelics. One polyol telechelic can be present in an amount of50-100% by weight. One or more aliphatic polyols as disclosed herein(e.g., C₃ to C₁₂ aliphatic polyols like 1,5-pentanediol,3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol,1,8-octanediol, 1,9-nonanediol, 1,10-decanediol), in an amount of 0-50%by weight, can be mixed with the polyol telechelic and then react withthe carbonate-forming compound. Small quantities of trimethylolethane,trimethylolpropane, and/or pentaerythritol may be mixed in forbranching. In one example, the starting polyol telechelic comprises atleast one polyol polyether formed from 50-100 mole % of at least a firstdiol and 0-50 mole % of at least a second diol, both independentlychosen from 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol,1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, tetrapropylene glycol, other oligomer diols of ethylene oxideand/or propylene oxide, and other aliphatic diols. In another example,the starting polyol telechelic comprises at least one fatty polyoltelechelic as disclosed herein.

The carbonate-forming compounds include, but are not limited to, diarylcarbonates, dialkyl carbonates, dicycloalkyl carbonates, diaryalkylcarbonates, dioxolanones, hexanediol bis-chlorocarbonates, phosgene andurea. Diaryl carbonates include diphenyl-, ditolyl-, dixylyl-, anddinaphthyl-carbonates. Dialkyl carbonates include those having linear orbranched C₁ to C₈ alkyl, cyclic, or alicyclic groups, such as dimethyl-,diethyl-, dipropyl-, dibutyl-, diamyl-, and dicyclohexyl-carbonates.Dioxolanones include ethylene carbonate, propylene carbonate, butylenecarbonate, glycerine carbonate, 4-chloro-1,3-dioxolan-2-one,4-hydroxymethyl-1,3-dioxolan-2-one, 4-phenyl-1,3-dioxolan-2-one,4-methoxymethyl-1,3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one,other cyclic carbonates as disclosed herein, substituted (such as alkyl)cyclic carbonates. Others include hexane-1,6-diol bis-chlorocarbonate,phosgene, and urea. The carbonate-forming compound is used in a defineddeficient quantity such that the desired molecular weight according tothe following equation results:

M _(w)(reaction product)=n×M _(w)(starting polyol telechelic)+(n−1)×26

where n is the number of moles of starting polyol telechelic or blend ofpolyol telechelic and aliphatic polyol; n−1 is the number of moles ofcarbonate-forming compound used; and 26 is the molecular weight of thecarbonyl group minus 2.

The reaction product can be polyol polyethercarbonates having M_(w) ofabout 500-12,000, such as about 700, about 1,000, about 2,000, about2,500, about 3,000, about 5,000, about 6,000, or any numbertherebetween, in which a ratio of ether linkages to carbonate linkagesis about 5:1 to about 1:5, such as about 3:1 to about 1:3, and thevarious alkylene units are arranged statistically, alternately, and/orblockwise. The polyol polyethercarbonates can have a hydroxyl number ofabout 30 or greater, such as about 50, about 60, about 75, about 80,about 100, or greater, or any number therebetween. Some of these polyolpolyethercarbonates can be low-melting waxes, having a softening pointof less than about 40° C., and a viscosity at 50° C. of about 8,500 orless, such as about 5,000, about 3,500, about 2,000, about 600, or less,or any number therebetween. Some of these polyol polyethercarbonates canbe liquid at room temperature (e.g., 20-25° C.). These polyolpolyethercarbonates can be high in hydrophobicity, hydrolysisresistance, and saponification resistance. Materials and methods used toproduce such polyol polyethercarbonates are disclosed in U.S. Pat. Nos.4,808,691 and 5,621,065, which are incorporated herein by reference.

l) Derivatized Polyol Telechelics

Polyol telechelics can be derived from corresponding polyacids and alkyl(such as methyl) esters thereof, such as through hydrogenation. Anycarboxylic acid terminated polymers known and/or available to oneskilled in the art, including the fatty polyacids and polyacid adductsdisclosed herein, may be converted to polyol telechelics. Other polyoltelechelics can be derived from suitable polymers, optionally having twoor more functionalities such as amine, hydroxyl, carbonyl, etc., throughreactions with polyols, aminoalcohols, hydroxy acids or esters thereof,cyclic ethers, and/or cyclic esters. For example, polyol telechelics canbe derived from polyamine telechelics or other polyol telechelics viareactions with cyclic esters, hydroxy acids, and/or hydroxy esters, inwhich multiple amide linkages or esters linkages, respectively, areformed.

One example of polyetherester polyols have a generic structure of:

where R₃ to R₄ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, or alkoxy moieties having about 1-60carbon atoms, such as about 1-20 carbon atoms; R₅ is a hydrogen, alkylgroup (such as methyl), phenyl group, halide, or mixture thereof, n isabout 1-12; and x is about 1-200. These polyetherester polyols can beobtained from polyol polyethers through means such as reaction withhydroxy acids or cyclic esters. Other polyetherester polyols can beformed from polyacid telechelics by reacting with polyols and/or cyclicesters.

One group of derivatized polyol telechelics can be prepared by addingcyclic ethers to the termini of an existing polyol telechelic. Forexample, the existing polyol telechelic can be any of the polyoltelechelics disclosed herein, such as one or a blend of the fatty polyoltelechelics, and the cyclic ethers can be one or more of those havingabout 2-14 carbon atoms, such as ethylene oxide, propylene oxide,butylene oxide, tetrahydrofuran, and cyclic ethers having 5 or morecarbon atoms. Known methods may be used to add the cyclic ethers to thepolyol telechelic. For example, the hydroxyl groups in the polyoltelechelic can be converted to alcoholate by heating with alkalihydroxide (such as NaOH or KOH) at about 100-140° C., which is thenmixed with the cyclic ether (such as those having a 3-membered ring) toinitiate an anionic polymerization. Alternatively, the cyclic ether(such as those having a 5-membered ring) is subjected to a cationicring-opening polymerization at about 0° C., in the presence of catalystssuch as boron trifluoride ether salt, and then mixed with alkali saltsof the polyol telechelic (such as disodium salt of the dimer diol) toterminate the polymerization and yield the derivatized polyoltelechelic.

The resulting polyol telechelic can have a structure ofHO—(Y—O)_(m)—X—O-(Z-O)_(n)—H, where X is the backbone of the startingpolyol telechelic HO-Z-OH; Y is the organic moiety of cyclic ether

Z is the organic moiety of cyclic ether

m and n are the same or different numbers of 0 or more, and m+n is about2-100, such as about 2-40. Y and Z can be the same or different, and canhave 2 or more carbon atoms or 5 or more carbon atoms. Y and Z canindependently have one or more heteroatoms such as O, S, N, and Si. Theresulting polyol telechelic can have a hydroxyl number of about 200 orless, such as about 140 or less. The molecular weight of segment Z-O canbe at least about 1% by weight of the M_(w) of the polyol telechelic,the latter of which can be about 500-20,000, such as about 600, about1,000, about 2,000, about 3,000, about 5,000, about 8,000, about 10,000,about 12,000, about 15,000, and any number therebetween. When certaincyclic ethers such as propylene oxide and butylene oxide are used, thehydroxyl groups of the resulting polyol telechelics may be secondary,which can be converted to primary for improved reactivity. These andother polyol telechelics as described in U.S. Pat. No. 6,252,037 areincorporated herein by reference.m) Ethylenically and/or Acetylenically Unsaturated Polyol Telechelics

Any of the polyol telechelics disclosed herein above may comprise one,two, or a plurality of ethylenic and/or acetylenic unsaturationmoieties. These unsaturation moieties can be used to form carbon-carbonand/or ionic crosslinks in combination with vulcanizing agents (i.e.,radical initiators, polyisocyanates, co-crosslinking agents, curativescomprising ethylenic and/or acetylenic unsaturation moieties, and/orprocessing aids). These unsaturation moieties may be pendant along thebackbone of the polyol telechelics, attached to pendant groups or chainsbranched off the backbone, and/or attached to the amine end-groups ofthe polyol telechelics.

For example, ethylenically and/or acetylenically unsaturated polyolpolyhydrocarbons include, without limitation, those having high or lowvinyl polyolefin backbones. These backbones can be formed from one ormore diene monomers, optionally with one or more other hydrocarbonmonomers. Exemplary diene monomers include conjugated dienes containing4-12 carbon atoms, such as 1,3-butadiene, isoprene, chloroprene,2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene,3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene,phenyl-1,3-butadiene, and the like; non-conjugated dienes containing5-25 carbon atoms such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene,2,5-dimethyl-1,5-hexadiene, 1,4-octadiene, and the like; cyclic dienessuch as cyclopentadiene, cyclohexadiene, cyclooctadiene,dicyclopentadiene, and the like; vinyl cyclic enes such as1-vinyl-1-cyclopentene, 1-vinyl-1-cyclohexene, and the like;alkylbicyclononadienes such as 3-methylbicyclo-(4,2,1)-nona-3,7-diene,and the like, indenes such as methyl tetrahydroindene, and the like;alkenyl norbornenes such as 5-ethylidene-2-norbornene,5-butylidene-2-norbornene, 2-methallyl-5-norbornene,2-isopropenyl-5-norbornene, 5-(1,5-hexadienyl)-2-norbornene,5-(3,7-octadienyl)-2-norbornene, and the like; and tricyclodienes suchas 3-methyltricyclo (5,2,1,0^(2,6))-deca-3,8-diene and the like.

Non-limiting examples of vinyl polyolefin backbones are vinylpolybutadienes, vinyl polyisoprenes, vinyl polystyrenebutadienes, vinylpolyethylenebutadienes, vinyl poly(styrene-propylene-diene)s, vinylpoly(ethylene-propylene-diene)s, and fluorinated or perfluorinatedderivatives thereof. High 1,2-vinyl content can be at least about 40%,such as 50%, 60%, 70%, 80%, 90%, or even greater. Low 1,2-vinyl contentcan be less than about 35%, such as 30%, 20%, 15%, 12%, 10%, 5%, or evenless. The vinyl polyolefin backbone can have various combinations ofcis-, trans-, and vinyl structures, such as having a trans-structurecontent greater than cis-structure content and/or 1,2-vinyl structurecontent, having a cis-structure content greater than trans-structurecontent and/or 1,2-vinyl structure content, or having a 1,2-vinylstructure content greater than cis-structure content or trans-structurecontent.

Other ethylenically and/or acetylenically unsaturated moieties that maybe incorporated onto the backbone of the polyol telechelics includeallyl groups and α,β-ethylenically unsaturated C₃ to C₈ carboxylategroups. Non-limiting examples of such ethylenically unsaturated moietiesinclude acrylate, methacrylate, fumarate, β-carboxyethyl acrylate,itaconate, and other unsaturated carboxylates disclosed herein. Theseunsaturated moieties can be attached to the hydroxyl groups on thepolyol telechelics by forming ester linkages. The incorporation of theseunsaturated moieties may take place before the formation of prepolymer,or after the prepolymer is reacted with stoichiometrically excessiveamounts of polyamine and/or polyol curatives.

Ethylenically and/or acetylenically unsaturated polyol polyhydrocarbonscan be liquid at ambient temperature, such as those having vinylpolybutadiene homopolymers or copolymers as backbones, and can have lowto moderate viscosity, low volatility and emission, high boiling point(such as greater than 300° C.), and molecular weight of about 1,000 toabout 5,000, such as about 1,800 to about 4,000, or about 2,000 to about3,500.

Polyols

Polyols include, but are not limited to, unsaturated diols such as1,3-bis(2-hydroxyethoxy) benzene, 1,3-bis[2-(2-hydroxyethoxy)ethoxy]benzene, N,N-bis(β-hydroxypropyl)aniline,1,3-bis{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy} benzene,hydroquinone-di(β-hydroxyethyl)ether,resorcinol-di(β-hydroxyethyl)ether; saturated diols such as ethyleneglycol, diethylene glycol, polyethylene glycol, propylene glycol,dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol,1,2-, 1,3-, 1,4-, or 2,3-butanediols, 2-methyl-1,4-butanediol,2,3-dimethyl-2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol,dimethylolcyclohexane, 1,3-bis(2-hydroxyethoxy)cyclohexane,1,3-bis[2-(2-hydroxyethoxy)ethoxy]cyclohexane,1,3-bis{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}cyclohexane; unsaturatedtriols such as castor oil (i.e., triricinoleoyl glycerol); saturatedtriols such as 1,2,4-butanetriol, 1,2,6-hexanetriol, trimethylolethane(i.e., 1,1,1-tri(hydroxymethyl)ethane), trimethylolpropane (i.e.,2,2-di(hydroxymethyl)-1-butanol), triethanolamine, triisopropanolamine;unsaturated tetraols such as2,4,6-tris(N-methyl-N-hydroxymethyl-aminomethyl)phenol; saturatedtetraols such as pentaerythritol (i.e., tetramethylolmethane),tetrahydroxypropylene ethylenediamine (i.e.,N,N,N′,N′-tetrakis(2-hydroxypropyl)-ethylenediamine); and other polyolssuch as mannitol (i.e., 1,2,3,4,5,6-hexanehexyl) and sorbitol (anenantiomer of mannitol) (both saturated).

The polyols can be alkanediols such as, without limitation, ethyleneglycol, 1-phenyl-1,2-ethanediol, 1,2- or 1,3-propanediol,3-chloro-1,2-propanediol, 2-methyl-1,3-propanediol,2,2-dimethyl-1,3-propanediol, 2,2-diphenyl-1,3-propanediol,2-ethyl-2-methyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol,1,3-, 1,4-, or 2,3-butanediol, 2-methyl-1,4-butanediol,1,1,4,4-tetraphenyl-1,4-butanediol,2,2,4,4,-tetramethyl-1,3-cyclobutanediol, 1,5- or 2,4-pentanediol,2-methyl-2,4-pentanediol, 1,6- or 2,5-hexanediol,2-ethyl-1,3-hexnaediol, 2,5-dimethyl-2,5-hexanediol,1,4-cyclohexanediol, 1,7-heptanediol, 1,8-octanediol, 1,12-dodecanediol,hydroquinone di(b-hydroxyethyl)ether, hydroquinonedi(b-hydroxypropyl)ether, resorcinol di(b-hydroxyethyl)ether, resorcinoldi(b-hydroxypropyl)ether, 2,2-bis(4-hydroxyphenyl)propane, and mixturesthereof. Fatty polyols include fatty diols and fatty triols such as1,9,10-trihydroxyoctadecane.

The polyol may have a structure of:

where Z₁ to Z₈ are independently chosen from halogenated orun-halogenated hydrocarbon moieties having about 1-20 carbon atoms,halogenated or un-halogenated organic moieties having at least one O, N,S, or Si atom and zero to about 12 carbon atoms, or halogens; Y₁ to Y₄are independently chosen from hydrogen, halogenated or un-halogenatedhydrocarbon moieties having about 1-20 carbon atoms, halogenated orun-halogenated organic moieties having at least one O, N, S, or Si atomand zero to about 12 carbon atoms, and halogens; Z is halogenated orun-halogenated hydrocarbon moieties having about 1-60 carbon atoms, orhalogenated or un-halogenated organic moieties having at least one O, N,S, or Si atom and zero to about 60 carbon atoms. Z can have one of thestructures (41)-(48) above. Other non-limiting examples include1,4-durene diol and 2,3,5,6-tetramethyl-1,4-dihydroxycyclohexane.

Aminoalcohol Telechelics

As used herein, the term “aminoalcohol telechelic” refers to telechelicpolymers having at least one terminal amine end-group and at least oneterminal hydroxyl end-group. Any such aminoalcohol telechelics availableto one of ordinary skill in the art are suitable for use in compositionsof the present disclosure. These telechelics can be linear, branched,block, graft, monodisperse, polydisperse, regular, irregular, tactic,isotactic, syndiotactic, stereoregular, atactic, stereoblock,single-strand, double-strand, star, comb, dendritic, and/or ionomeric,and include homopolymers, random copolymers, pseudo-copolymers,statistical copolymers, alternating copolymers, periodic copolymer,bipolymers, terpolymers, quaterpolymers, as well as derivatives of anyand all polyamine telechelics, polyol telechelics, and polyacidsdisclosed herein. Aminoalcohol telechelics can have any of the polymeror copolymer structures of the herein-described polyamine telechelicsand polyol telechelics, such as polyhydrocarbons (such as polydienes),polyethers, polyesters (such as polycaprolactones), polyamides (such aspolycaprolactams), polycarbonates, polyacrylates (such aspolyalkylacrylates), polysiloxanes, and copolymers thereof.

The aminoalcohol telechelic can be reaction product of polyaminetelechelic and cyclic ester, or blend of cyclic ester and cyclic amide.The polyamine telechelic can serve as base to open the cyclic ringstructures. Any of the polyamine telechelics, cyclic esters, and cyclicamides as disclosed herein are suitable. The polyamine telechelics canhave a molecular weight of about 1,000-5,000, such as about 2,000-4,000,having aliphatic primary amine end-groups, and include polyetherpolyamines such as diamines and triamines of polyoxyethylene,polyoxypropylene, and poly(oxyethylene-co-oxypropylene). Commerciallyavailable polyether polyamines include Jeffamine® D-2000 and D-3000. Thecyclic esters and cyclic amides have a generic structure of:

where A is O or N, n is 0 to about 4, such as about 2 or about 3.Commercially, caprolactone, caprolactone diols, and caprolactone triolsare available under the trademark Tone® from Union Carbide Chemicals andPlastics Technology Corporation of Danbury, Conn.

The aminoalcohol telechelics can be in situ polymerization productsformed during the synthesis of isocyanate-terminated prepolymer, inwhich the polyamine telechelic, the cyclic ester and/or amide, andpolyisocyanate (such as uretdione dimers and/or isocyanurate trimers)are mixed together. An exothermic reaction can result in the prepolymerhaving a linear aliphatic backbone, with the chain structure of thepolyamine telechelic on one side and linked to a first polyisocyanatemolecule via a urea linkage, and a polycaprolactone chain on the otherside and linked to a second polyisocyanate molecule via a urethanelinkage. Methods of forming the prepolymer are detailed in U.S. Pat. No.6,437,078, which is incorporated herein by reference.

Aminoalcohols

Aminoalcohols useful in the present disclosure include any and allmonomers, oligomers, and polymers having at least one freeisocyanate-reactive hydroxy group and at least one freeisocyanate-reactive amine group. The hydroxy and amine groups may beprimary or secondary, terminal or pendant groups on the oligomeric orpolymeric backbone, and in the case of secondary or tertiary aminegroups, may be embedded within the backbone. Aminoalcohols can be linearor branched, saturated or unsaturated, aliphatic, alicyclic, aromatic,or heterocyclic. The aminoalcohol can be R—[HN—(R′O)_(x)]_(y)—H, where Ris hydrogen, hydrocarbyl or hydroxyhydrocarbyl group (such as —R′—OH)having about 1-12 carbon atoms, such as about 1-8 or about 1-4 carbonatoms; R′ is a divalent hydrocarbyl moiety having about 2-30 carbonatoms; each x is independently about 1-15; and y is about 1-3. R and R′can independently be acyclic, alicyclic or aromatic. These aminoalcoholsinclude alkanolamines, N-(hydroxyhydrocarbyl)amines,hydroxypoly(hydrocarbyloxy)amines, and hydroxypoly(hydroxyl-substitutedoxyalkylene)amines, conveniently prepared by reaction of one or moreepoxides with amines, and are also known as alkoxylated amines (when yis 1) or diamines (when y is 2).

R′ can be linear or branched alkylene having about 2-30 carbon atoms,such as about 4 or 6 carbon atoms or any number therebetween, likeethylene, propylene, 1,2-butylene, 1,2-octadecylene, etc. R can bemethyl, ethyl, propyl, butyl, pentyl, or hexyl group. Non-limitingexamples of these alkanolamines include monoethanolamine,diethanolamine, diethylethanolamine, ethylethanolamine,monoisopropanolamine, diisopropanolamine, butyldiethanolamine, etc.Non-limiting examples of hydroxyhydrocarbylamines include2-hydroxyethylhexylamine, 2-hydroxyethyloctylamine,2-hydroxyethylpentadecylamine, 2-hydroxyethyloleylamine,2-hydroxyethylsoyamine, 2-hydroxyethoxyethylhexylamine, and mixturesthereof.

The aminoalcohol can be hydroxy-containing polyamine, such as analogs ofhydroxy monoamines, like alkoxylated alkylenepolyamines (e.g.,N,N-(diethanol)ethylene diamines). Such polyaminoalcohols can beprepared by reacting one or more cyclic ethers such as those disclosedherein with the diamines and higher polyamines disclosed herein, such asalkylene polyamines, or with the various aminoalcohols, such as thosedisclosed herein, including primary, secondary, and tertiaryalkanolamines, with a molar ratio of about 1:1 to about 2:1. Reactantratios and temperatures for carrying out such reactions are known tothose skilled in the art. Specific examples of hydroxy-containingpolyamines include N-(2-hydroxyethyl)ethylenediamine,N,N′-bis(2-hydroxyethyl)ethylenediamine, 1-(2-hydroxyethyl)piperazine,mono(hydroxypropyl)-substituted tetraethylenepentamine,N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtainedby condensation of the above-illustrated hydroxy-containing polyaminesthrough amine and/or hydroxyl groups are likewise useful. Condensationthrough amine groups can result in a higher amine accompanied by removalof ammonia while condensation through the hydroxyl groups can result inproducts containing ether linkages accompanied by removal of water.

Other examples of aminoalcohols includeN-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclopentylamine,parahydroxyaniline, 2-propanol-1,1′-phenylaminobis,N-hydroxyethylpiperazine, 2-aminoethanol, 3-amino-1-propanol,1-amino-2-propanol, 2-(2-aminoethoxy)ethanol,2-[(2-aminoethyl)amino]ethanol, 2-methylaminoethanol,2-(ethylamino)ethanol, 2-butylaminoethanol, diethanolamine,3-[(hydroxyethyl)amino]-1-propanol, diisopropanolamine,bis(hydroxyethyl)-aminoethylamine, bis(hydroxypropyl)-aminoethylamine,bis(hydroxyethyl)-aminopropylamine, bis(hydroxypropyl)-aminopropylamine,hydroxy-functional amino acids as described herein, and mixturesthereof.

Polyacids

As used herein, the term “polyacids” encompasses diacids, triacids,tetracids, other higher acids, as well as acid anhydrides, dianhydrides,chlorides, esters, dimers, trimers, oligomers, polymers, and any otherstructures capable of forming at least two ester or amide linkages.Suitable organic polyacids include, but are not limited to, organicmonomeric diacids having about 2-60 carbon atoms, such as branched orlinear aliphatic dicarboxylic acids having about 2-44 carbon atoms,alkane dicarboxylic acids having about 6-22 carbon atoms, cyclic orcycloaliphatic dicarboxylic acids having about 6-44 carbon atoms, andaromatic dicarboxylic acids having about 8-44 carbon atoms. Thepolyacids can be aliphatic dicarboxylic acids and alicyclic dicarboxylicacids having para-, meta- and/or ortho-positioned dicarboxylic acidmoieties.

Non-limiting examples of polyacids include unsaturated aliphaticdicarboxylic acids such as maleic acid, fumaric acid, itaconic acid,citraconic acid, and mesaconic acid; saturated aliphatic polycarboxylicacids such as oxalic acid, malonic acid, glyceric acid, dimethyl malonicacid, succinic acid, methylsuccinic acid, diglycolic acid, glutaricacid, 3-methylglutaric acid, 2,2- and 3,3-dimethylglutaric acid, adipicacid, 2,2,4- and 2,4,4-trimethyladipic acid, pimelic acid, suberic acid,azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid,brassylic acid, tetradecanedioic acid, pentadecanedioic acid,heptadecanedioic acid, heptadecanedioic acid, octadecanedioic acid,heptadecanedicarboxylic acid, octadecanedicarboxylic acid,nonadecanedicarboxylic acid, and eicosanedicarboxylic acid; alicyclicdicarboxylic acids such as 1,1-cyclopropanedicarboxylic acid,1,3-cyclopentanedicarboxylic acid, 1,2- and 1,4-cyclohexanedicarboxylicacid, 4,4′-dicaboxydicyclohexylrnethane,3,3′-dimethyl-4,4′-dicarboxydicyclohexylmethane,4,4′-dicarboxydicyclohexylpropane, 1,4-bis(carboxymethyl)cyclohexane,2,3-, 2,5-, and 2,6-norbornanedicarboxylic acid, tetrahydrophthalicacid, hexahydrophthalic acid, hexahydroterephthalic acid,hexahydroisophthalic acid, and hexahydronaphthalic acid; aromaticdicarboxylic acids such as phthalic acid, isophthalic acid,tributylisophthalic acid, terephthalic acid, nitrophthalic acid,5-methylisophtalic acid, 2-methylterephtalic acid, 2-chloroterephtalicacid, naphthalic acid, diphenic acid, 4,4′-diphenyldicarboxylic acid,4,4′-oxydibenzoic acid, and 1,3-phenylenedioxy diacetic acid;tricarboxylic acids, tetracarboxylic acids, and the like, such ashexanetricarboxylic acid, hexanetetracarboxylic acid,1,2,3,4-cyclobutanetetracarboxylic acid,2,2-dimethylcyclobutane-1,1,3,3-tetracarboxylic acid,1,2,3,4-cyclopentanetetracarboxylic acid,cis,cis-1,3,5-trimethyl-cyclohexane-1,3,5-tricarboxylic acid, aconiticacid, 1,2,3-benzenetricarboxylic acid, trimellitic acid, trimesic acid,2-methylbenzene-1,3,5-tricarboxylic acid, pyromellitic acid,3,4,3′,4′-biphenyltetracarboxylic acid,2,3,3′,4′-biphenyltetracarboxylic acid, and mellitic acid.

Non-limiting examples of acid anhydrides include aliphatic diacidanhydrides such as maleic anhydride, itaconic anhydride, and citraconicanhydride; aromatic diacid anhydrides such as phthalic anhydride.Non-limiting examples of acid dianhydrides include pyromelliticdianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, and3,3,4,4-biphenyltetracarboxylic dianhydride. Non-limiting examples ofcarboxylic acid (co)polymers, which can have M_(n) of about1,000-15,000, include dicarboxy-terminated polybutadienes,poly(meth)acrylic acids, polyitaconic acids, copolymers of (meth)acrylicacid and maleic acid, copolymers of (meth)acrylic acid and styrene,dicarboxy-terminated poly(dimethylsiloxane-co-diacid), anddicarboxy-terminated poly(dimethylsiloxane-co-dimer acid).

The polyacid may further contain various moieties such as, but are notlimited to, heterocyclic rings, nitro groups, amine groups, iminegroups, carbonyl groups, hydroxyl groups, ether bonds, ester bonds,amide bonds, imide groups, urethane bonds, urea bonds, and/or ionicgroups. Non-limiting examples of ketodiacids are oxaloacetic acids, 2-and 3-oxoglutaric acid, and dimethyl-3-oxoglutaric acid. Non-limitingexamples of heterocyclic diacids are dinicotinic acid, dipicolinic acid,lutidinic acid, quinolinic acid, and pyrazine-2,3-dicarboxylic acid.Ionic groups can be anionic groups, such as carboxylates, sulfonates,and phosphates. Non-limiting examples are alkali metal salts ofsulfoisophthalic acid, such as sodium 3-sulfoisophthalate and potassium3-sulfoisophthalate. Other useful polyacids include salts of tri- ortetrasulfonic acids, such as trisodium salt ofnaphthalene-1,3,6-trisulfonic acid, the trisodium salt of8-tetradecyloxypyrene-1,3,6-trisulfonic acid, and the tetrasodium saltof pyrene-1,3,6,8-tetrasulfonic acid.

Fatty Polyacids

Fatty polyacids can be derived from monounsaturated and/orpolyunsaturated fatty acids through reactions involving the doublebonds, such as ozonolysis (e.g., forming azelaic acid from oleic acid),caustic oxidation (e.g., forming sebacic acid from ricinoleic acid orcastor oil), and polymerization (e.g., dimerization). Polymeric fattyacids can be formed from a polymerization reaction of a saturated,ethylenically unsaturated, or acetylenically unsaturated fatty acid andat least one compound to provide a second acid moiety or a functionalgroup convertible to the second acid moiety. Polymeric fatty acids mayresult from the polymerization of oils or free acids or esters thereof,via dienic Diels-Alder reaction to provide a mixture of dibasic andhigher polymeric fatty acids. In place of these methods ofpolymerization any other method of polymerization may be employed,whether the resultant polymer possesses residual unsaturation or not.

Fatty acids can be long-chain monobasic fatty acids having a C₆ orlonger chain, such as C₁₁ or longer or C₁₆ or longer, and C₂₄ orshorter, such as C₂₂ or shorter. Unsaturated fatty acids and estersthereof can be monounsaturated and/or polyunsaturated, monocarboxylicand/or polycarboxylic, and include, without limitation, oleic acid,linoleic acid, linolenic acid, palmitoleic acid, elaidic acid, erucicacid, hexadecenedioic acid, octadecenedioic acid, vinyl-tetradecenedioicacid, eicosedienedioic acid, dimethyl-eicosedienedioic acid,8-vinyl-10-octadecenedioic acid, methyl, ethyl, and other esters (suchas linear or branched alkyl esters) thereof, and mixtures thereof. Alsodimerizable are fatty acid mixtures obtained in the hydrolysis ofnatural fats and/or oils, such as olive oil fatty acids, sunflower oilfatty acids, soybean fatty acids, corn oil fatty acids, canola fattyacids, cottonseed oil fatty acids, coriander oil fatty acids, tallowfatty acids, coconut fatty acids, rapeseed oil fatty acids, fish oilfatty acids, tall oil fatty acids, methyl, ethyl, and other estersthereof, and mixtures thereof.

The polymeric fatty acids can be adduct acid, such as adduct diacidformed between a conjugated ethylenically unsaturated fatty acid (e.g.,linoleic acid, soybean oil fatty acid, tall oil fatty acid) and ashort-chain unsaturated acid (e.g., acrylic acid, methacrylic acid,crotonic acid). Methods for producing such adduct acids are described,for example, in U.S. Pat. Nos. 5,136,055, 5,053,534, 4,156,095, and3,753,968. Alternatively, the polymeric fatty acid can be obtained byhydroformylating an unsaturated fatty acid and then oxidizing it intofatty dicarboxylic acid. For example, oleic acid can be reacted withcarbon monoxide and hydrogen to form 9(10)-formyloctadecanoic acid,which can then be oxidized to 9(10)-carboxyoctadecanoic acid.

Polymeric fatty acids may also be obtained in known manners (e.g.,addition polymerization using heat and a catalyst) from one monobasicfatty acid or a blend of two or more monobasic fatty acids, themonobasic fatty acids being saturated, ethylenically unsaturated, oracetylenically unsaturated. The resulting polymeric fatty acids areoften referred to in the art as dimers (i.e., dimerized fatty acids),trimers (i.e., trimerized fatty acids) and so forth (e.g., oligomericfatty acids). Saturated monobasic fatty acids can be polymerized atelevated temperatures with a peroxidic catalyst such as di-t-butylperoxide. Suitable saturated monobasic fatty acids include linear orbranched acids such as caprylic acid, pelargonic acid, capric acid,lauric acid, myristic acid, palmitic acid, isopalmitic acid, stearicacid, arachidic acid, behenic acid, and lignoceric acid.

Ethylenically unsaturated monobasic fatty acids and esters thereof canbe polymerized via non-catalytic polymerization at a higher temperature,or using catalysts such as acid or alkaline clays, di-t-butyl peroxide,boron, trifluoride and other Lewis acids, anthraquinone, sulfur dioxideand the like. Methods of dimerizing unsaturated fatty acids and theiresters are described in U.S. Pat. No. 6,187,903, among others. Suitablemonomers include linear or branched acids having at least oneethylenically unsaturated bond, such as about 2-5 of such bonds, like3-octenoic acid, 11-dodecanoic acid, linderic acid, oleic acid, linoleicacid, linolenic acid, hiragonic acid, eleostearic acid, punicic acid,catalpic acid, licanoic acid, clupadonic acid, clupanodonic acid,lauroleic acid, myristoleic acid, tsuzuic acid, palmitoleic acid,gadoleic acid, cetoleic acid, nervonic acid, moroctic acid, timnodonicacid, arachidonic acid (i.e., eicosatetraenoic acid), nisinic acid,scoliodonic acid, and chaulmoogric acid.

Acetylenically unsaturated monobasic fatty acids can be polymerized bysimply heating the acid. The polymerization of these highly reactivematerials can occur in the absence of a catalyst. Any acetylenicallyunsaturated fatty acid, linear or branched, mono-unsaturated orpoly-unsaturated, are useful monomers for the preparation of polymericfatty acids. Suitable examples of such materials include 10-undecynoicacid, tariric acid, stearolic acid, behenolic acid and isamic acid.

Polymerization reaction of the monobasic fatty acids as described above,include so-called dimeric fatty acids, are commonly structural isomermixtures containing a predominant proportion (about 45-95% by weight orgreater) of aliphatic and alicyclic dimer diacids (such as C₃₆ or C₄₄diacids), a small quantity (about 1-35% by weight) of trimer acids andhigher polymeric fatty acids (such as C₅₄₊ polyacids), and some (up toabout 20% by weight) residual monomers (such as C₁₈ or C₂₂ branchedchain monoacids). The ratio between the reactants in the disclosedprocess is known in the art as a topological ratio. Commercial productsof these polymeric fatty acids can contain about 75-95% by weight ofdimeric acids, about 4-22% by weight of trimeric acids, about 1-3% byweight of monomeric acid. The molar ratio of dimeric to trimeric acidcan be about 5:1 to about 36:1. The relative ratios of monomer, dimer,trimer and higher polymer in un-fractionated dimer acid can be dependenton the nature of the starting materials and the conditions ofpolymerization and subsequent distillation.

Dimerized fatty acids may be “crude”, i.e., obtained directly fromdimerization without distillation, or refined to increase dimerconcentration. Refined dimerized acids such as partially or fullyhydrogenated dimer fatty acids can have a dimer content of about 95% byweight or greater, such as at least about 97%, a monomer content ofabout 1%, a trimer content of about 3%, an acid value of about 193-201,a saponification value of about 198, and an iodine value of about 95.Hydrogenated dimer fatty acids can reduce aesthetically unpleasingcolor. The degree of hydrogenation can correspond to an iodine value ofabout 110 or less, such as about 95 or less, according to ASTM D1959-97or D5768-02. The fatty polyacids, such as the dimer diacids and diestersthereof, can be substantially free of interesters, the presence of whichmay hinder subsequent polymerization reactions. Methods for reducinginterester content in fatty polyacids include hydrolysis/extraction asdisclosed in U.S. Pat. No. 6,187,903, which is incorporated herein byreference. The fatty polyacids or esters thereof can have an interestercontent of about 0.2% by weight or less, such as about 0.05% or less.

Dimer diacids may be unsaturated, partly hydrogenated, or completelyhydrogenated (i.e., fully saturated). Non-limiting dimer diacids canhave one of the following structures:

where R is the same or different moieties chosen from hydrogen, alkyl,aryl, aralkyl, alicyclic, cycloalkyl, and alkoxy groups; x+y and m+n areboth at least about 8, such as at least about 10, such as 12, 14, 15,16, 18, 19, or greater.

Fatty polyacids can have at least one divalent hydrocarbon radicalhaving at least 30 carbon atoms, such as 36-180 carbon atoms, which canbe linear, branched, cyclic, and/or substituted, such asmonocycloaliphatic moiety having a 6-membered carbon ring (e.g.,cyclohexene ring), bicycloaliphatic moiety having a 10-membered carbonring, and substituted aliphatic moiety (e.g., halogenated aliphaticmoiety such as fluoroaliphatic polyacids). Fatty polyacids such as dimerdiacids can have an acid value of 150-250, such as 170-200 or 190-200, asaponification value of 170-210, and a viscosity at 25° C. of 50,000 cStor less, such as 30,000 cSt or less, 10,000 cSt or less, 500 cSt orgreater, like 600 cSt, 7,500 cSt, 8,500 cSt, 9,000 cSt, and anyviscosity therebetween. Examples are available from HumKo Chemical ofMemphis, Tenn. Fatty polyacids can be branched, such as with linear orbranched alkyl groups. Fluid fatty polyacids can be used as reactivediluents in solvent-borne polyurethane/polyurea compositions to achievehigher solid content.

Polymeric fatty acids and other polyacids as described above, as well asmethods to produce such polyacids can be found in U.S. Pat. Nos.6,670,429, 6,310,174, 6,187,903, 5,545,692, 5,326,815, 4,937,320,4,582,895, 4,536,339, and 4,508,652, among others. To form reactivepolymers of the present disclosure, polymeric fatty acids or estersthereof can also be epoxidized, for example by reaction with peraceticacid, performic acid or with hydrogen peroxide and formic acid or aceticacid. Suitable epoxidized fatty acids and esters are described inBritish Patent Nos. 810,348 and 811,797. Dimer acids can be converted todimer diols, dimer diamines, and/or dimer diisocyanates, all of whichare suitable for the compositions of the present disclosure.

Amino Acids

Any and all amino acids known and/or available to one skilled in theart, which have at least one reactive amine group (such as primary aminegroup) and at least on acid group (such as carboxylic acid group), canbe used in the present disclosure. Also useful are cyclic amides of thecorresponding amino acids, and amino esters (such as methyl and ethylesters) of the corresponding amino acids. Amino acids can be linear orbranched, saturated or unsaturated, aliphatic, alicyclic, aromatic, orheterocyclic. Non-limiting examples of the aminocarboxylic acids canhave about 2-18 carbon atoms, and include glycine, alanine, valine,leucine, isoleucine, phenylalanine, sarcosine, asparagine, glutamine,glucoseamine, melamine, tryptamine, kynurenine, tyrosine, guanidine,polyguanides, ethylglutamic acid, carboxyglutamic acid, aspartic acid,methyl-aspartic acid, 4-aminobutyric acid, anthranilic acid,3-aminobenzoic acid, 4-aminobenzoic acid, 4-amino-2-salicylic acid,4-aminomethylbenzoic acid, 2-aminoadipic acid, alloxanic acid,ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid,ω-aminocapric acid, 11-aminoundecanoic acid, ω-aminolauric acid,13-aminotridecanoic acid, ω-aminomyristic acid, 15-aminopentadecanoicacid, lactams thereof, amino esters thereof, and mixtures thereof.

Hydroxy Acids

Any and all hydroxy acids known and/or available to one skilled in theart, which have at least one reactive hydroxyl group and at least onacid group (such as carboxylic acid group), are suitable for use in thepresent disclosure. Also useful are cyclic esters of the correspondingamino acids, and hydroxy esters (such as methyl and ethyl esters) of thecorresponding hydroxy acids. Hydroxy acids can be linear or branched,saturated or unsaturated, aliphatic, alicyclic, aromatic, orheterocyclic. Non-limiting examples of the hydroxycarboxylic acids canhave about 2-18 carbon atoms, and include benzilic acid, caffeic acid,ferulic acid, gallic acid, gentisic acid, isovanillic acid, mandelicacid, resorcylic acid, salicylic acid, tropic acid, vanillic acid,pamoic acid, malic acid, tartaric acid, citric acid, ascorbic acid,D,L-lactic acid, D-lactic acid, L-lactic acid, glycolic acid,hydroxy-functional amino acids as described above, and mixtures thereof.Also included are hydroxy acids of the corresponding cyclic compounds asdisclosed herein, such as cyclic esters and cyclic anhydrides.

Cyclic Esters and Cyclic Amides

Any and all cyclic esters and cyclic amides known and/or available toone skilled in the art are suitable for use in the present disclosure.Also useful are amino acids and esters thereof of the correspondingcyclic amides, and hydroxy acids and esters thereof of the correspondingcyclic esters. Cyclic esters and cyclic amides can be saturated orunsaturated, substituted or unsubstituted, and include lactones andlactams. Non-limiting examples of lactones can have about 4-20 carbonatoms, and include β-propiolactone, methyl propiolactone,bis(chloromethyl)propiolactone, β-butyrolactone, γ-butyrolactone,3-hydroxy-γ-butyrolactone, 4-hydroxy-3-pentenoic acid lactone,hydroxymethyl-butyrolactone, α-angelicalactone, β-angelicalactone,4-methyl-butyrolactone, γ-methyl-γ-butyrolactone, γ-hexylactone,γ-heptalactone, γ-octalactone, γ-nonalactone, γ-decalactone,γ-undecalactone, 3-methyl-γ-decalactone, γ-dodecalactone,β-valerolactone, γ-valerolactone, γ-hydroxy-valerolactone, mevalonicacid lactone, δ-valerolactone, methyl-δ-valerolactone,trimethoxyvalerolactone, δ-heptalactone, δ-octalactone, δ-nonalactone,δ-decalactone, δ-undecalactone, δ-dodecalactone, δ-tridecalactone,δ-tetradecalactone, ε-caprolactone, ε-caprolactone diol, ε-caprolactonetriol, γ-methyl-ε-caprolactone, ε-methyl-ε-caprolactone,β,δ-dimethyl-ε-caprolactone, β-methyl-ε-isopropyl-caprolactone,ε-decalactone, ε-undecalactone, ε-dodecalactone, γ-caprylolactone,γ-ethyl-γ-caprylolactone, ξ-enantholactone, ooctalactone, ω-nonalactone,ω-decalactone, ω-undecanolactone, ω-laurolactone, ω-tridecalactone,ω-tetradecalactone, (ω-pentadecalactone, ω-hexadecalactone,ω-heptadecalactone, ω-octadecalactone, neptalactone, ambrettolide,3-butylidenephthalide, 7-decen-1,4-lactone, 9-decen-5-olide,δ-2-decenolactone, δ-7-decenolactone, dihydroactinidiolide,dihydroambrettolide, 3,3-dimethyl-2-hydroxy-4-butanolide,3,4-dimethyl-5-pentyl-2(5H)-furanone, γ-6-dodecenolactone,dihydrocoumarin, 5-ethyl-3-hydroxy-4-methyl-2(5H)-furanone,5-(cis-3-hexenyl)dihydro-5-methyl-2(3H)-furanone,3-hydroxy-4,5-dimethyl-2(5H)-furanone, 5-hydroxy-8-undecenoic acidδ-lactone, jasmolactone, massoia lactone, menthone lactone,β-methyl-γ-octalactone, mintlactone, γ-2-nonenolactone,δ-octadecalactone, 4,4-dibutyl-γ-butyrolactone,6-hydroxy-3,7-dimethyloctanoic acid lactone, ω-6-hexadecenlactone,5-hydroxy-2,4-decadienoic acid δ-lactone, octahydrocoumarin,6-pentyl-α-pyrone, 3-propylidenephthalide, sclareolide,4-vinyl-γ-valerolactone, 2,3-dimethyl-2,4-nonadien-4-olide,2-buten-4-olide, 3,4-dimethyl-5-pentylidene-5H-furan-2-one,3-decen-4-olide, 3-methyl-trans-5-decen-4-olide, 3-nonen-4-olide,α-oxo-β-ethyl-γ-butyrolactone, β-methyl-γ-nonalactone,cis-7-decen-4-olide, 2-hydroxy-3,3-dimethyl-γ-butyrolactone,hexahydro-3,6-dimethyl-2(3H)-benzofuranone, γ-thiobutyrolactone, andmixtures thereof.

Non-limiting examples of lactams can have about 4-20 carbon atoms, andinclude propiolactam, N-methyl-β-propiolactam, N-phenyl-β-propiolactam,butyrolactam, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone,N-phenyl-2-pyrrolidone, N-t-butyl-2-pyrrolidone,N-methyl-5-methyl-2-pyrrolidone, valerolactam, N-methyl-2-piperidone,N-carbethoxy-2-piperidone, 4-chloro-N-methyl-2-piperidine,4-hydroxy-N-methyl-2-piperidine, N-vinyl-2-piperidone,N-phenyl-2-piperidone, N-acetyl-2-piperidone, N-t-butyl-2-piperidone,dimethyl-2-piperidone, caprolactam, N-methyl-ε-caprolactam,N-phenyl-ε-caprolactam, enantholactam, caprylolactam, undecanolactam,laurolactam, N-methyl-ω-laurolactam, N-vinyl-ω-laurolactam, halogenatedderivatives thereof, and mixtures thereof.

Other cyclic compounds that can be blended with the cyclic esters and/orcyclic amides for copolymerization or other reactions include, withoutlimitation, 1,4-dioxane-2-one, glycolide, lactides (i.e., D,L-lactide,D-lactide, and L-lactide), 1,4-dithiane-2,5-dione, cyclic oxalates suchas ethylene oxalate, propylene oxalate, butylene oxalate, hexamethyleneoxalate, and decamethylene oxalate, cyclic carbonates such as ethylenecarbonate, vinylene carbonate, 1,2-propylene carbonate, 1,3-propylenecarbonate, 2,2-dimethyl-trimethylene carbonate, 2,3-butylene carbonate,1,2-butylene carbonate, 1,4-butylene carbonate,1-isopropyl-2,2-dimethyl-1,3-propylene carbonate, neopentylenecarbonate, 3-methyl-pentamethylene carbonate, hexamethylene carbonate,octamethylene carbonate, cyclic anhydrides such as adipic anhydride.Diacrylic acid and/or dimethacrylic acid may be added.

Isocyanate Reactants

Any one or blend of two or more isocyanate-functional compoundsavailable to one of ordinary skill in the art may be suitable for use incompositions of the present disclosure. Isocyanate-functional compoundscan be organic isocyanates in general, and may have an isocyanatefunctionality of about 1 (i.e., monoisocyanates), such as about 2 orgreater (i.e., polyisocyanates). Polyisocyanates for use according tothe disclosure can include monomers, dimers (such as uretdiones ofidentical polyisocyanates and isocyanate derivatives of dimer acids ordimer amines), trimers (such as isocyanurates of identical or differentpolyisocyanates, isocyanate derivatives of trimer acids or trimeramines), tetramers, oligomers (of same or different monomers, orisocyanate derivatives of oligomer polyacids or oligomer polyamines),adducts (such as uretdiones of different polyisocyanates and isocyanatederivatives of adduct polyacids or adduct polyamines), polymers (such asisocyanate derivatives of polymer polyacids or polymer polyamines),polyisocyanate-terminated prepolymers, low-free-isocyanate prepolymers,quasi-prepolymers, isomers thereof, modified derivatives thereof, andcombinations thereof. Structure of the isocyanate reactant can partiallyor fully be substituted, unsubstituted, saturated, unsaturated,hydrogenated, aliphatic, alicyclic, cyclic, polycyclic, aromatic,araliphatic, heteroaliphatic, and/or heterocyclic.

Suitable polyisocyanates may have the generic structure of R(NCO)_(n),where n is about 2-4; R comprises one or more linear or branched,substituted or unsubstituted, saturated or unsaturated moieties havingabout 2-60 carbon atoms, such as aliphatic moieties of about 4-30 orabout 6-20 carbon atoms, cyclic or alicyclic moieties of about 6-40 orabout 6-30 carbon atoms, aromatic or araliphatic moieties of about 6-30or about 6-18 carbon atoms, and mixtures thereof. When multiple cyclicor aromatic moieties are present, linear and/or branched aliphatichydrocarbon moieties having about 1-20 or about 1-10 carbon atoms can bepresent as spacers separating adjacent ring structures. The cyclic oraromatic moieties may be substituted at 2-, 3-, 4- and/or otheravailable positions. Any available hydrogen atoms in the polyisocyanatecan also be substituted. Substituent moieties include, but are notlimited to, linear or branched aliphatic hydrocarbons; halogens; organicmoieties having one or more heteroatoms such as N, O, S, P, and/or Si(e.g., cyano, amine, silyl, hydroxyl, acid, ether, ester, etc.); or amixture (such as isomeric or racemic mixtures) thereof. Also includedare, for example, oligoisocyanates and polyisocyanates which can beprepared from the diisocyanates or triisocyanates listed or mixturesthereof by coupling by means of urethane, allophanate, urea, biuret,uretdione, amide, isocyanurate, carbodiimide, uretonimine,oxadiazinetrione, and/or iminooxadiazinedione structures.

Exemplary polyisocyanates include, without limitation, aromaticdiisocyanates such as p-phenylene diisocyanate (“PPDI,” i.e.,1,4-phenylene diisocyanate), m-phenylene diisocyanate (“MPDI,” i.e.,1,3-phenylene diisocyanate), o-phenylene diisocyanate (i.e.,1,2-phenylene diisocyanate), 4-chloro-1,3-phenylene diisocyanate,toluene diisocyanate (“TDI”), 2,2′-, 2,4′-, and 4,4′-biphenylenediisocyanates, 3,3′-dimethyl-4,4′-biphenylene diisocyanate (“TODI”),3,3′-dimethoxy-4,4′-biphenylene diisocyanate (i.e.,3,3′-dimethoxy-4,4′-diisocyanato-diphenyl), 2,2′-, 2,4′-, and4,4′-diphenylmethane diisocyanates (“MDI”), 2,2′-, 2,4′-, and4,4′-diphenyldimethylmethane diisocyanates, 2,2′-, 2,4′-, and4,4′-diphenylethane diisocyanates, 2,2′-, 2,4′-, and 4,4′-stilbenediisocyanates, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 1,4- and1,5-naphthalene diisocyanates (“NDI”), anthracene diisocyanate,tetracene diisocyanate, mixtures of MDI and PMDI, and mixtures of TDIand PMDI; araliphatic diisocyanates such as 1,2-, 1,3-, and 1,4-xylenediisocyanates (“OXDI,” “MXDI,” “PXDI”), m-tetramethylxylene diisocyanate(“m-TMXDI”), and p-tetramethylxylene diisocyanate (“p-TMXDI”); aliphaticdiisocyanates such as ethylene diisocyanate, 1,2- and 1,3-propylenediisocyanates, 1,2-, 1,3-, and 1,4-tetramethylene diisocyanates,1,5-pentamethylene diisocyanate, 2-methyl-1,5-pentamethylenediisocyanate, 1,6-hexamethylene diisocyanate (“HDI”) and isomersthereof, 2,4-dimethyl-hexamethylene diisocyanate (“DMHDI”) and isomersthereof, 2,2,4-trimethyl-hexamethylene diisocyanate (“TMDI”) and isomersthereof, 1,7-heptamethylene diisocyanate and isomers thereof,1,8-octamethylene diisocyanate and isomers thereof, 1,9-novamethylenediisocyanate and isomers thereof, 1,10-decamethylene diisocyanate andisomers thereof, 1,12-dodecane diisocyanate and isomer thereof,bis(isocyanatomethyl)cyclohexane (i.e., 1,4-cyclohexane-bis(methyleneisocyanate)), 2,4′- and 4,4′-bis(isocyanatomethyl) dicyclohexanes,isocyanatomethylcyclohexane isocyanate, isocyanatoethylcyclohexaneisocyanate, and lysine alkyl (C₁₋₁₀) ester diisocyanate; alicyclicdiisocyanates such as 1,3-cyclobutane diisocyanate, 1,2-, 1,3-, and1,4-cyclohexane diisocyanates, 2,4- and 2,6-methylcyclohexanediisocyanates (“HTDI,” i.e., 2,4- and 2,6-hexahydrotoluenediisocyanates), 2,2′-, 2,4′-, and 4,4′-dicyclohexylmethane diisocyanates(“H₁₂MDI,” i.e., bis(isocyanatocyclohexyl)-methane), 2,4′- and4,4′-dicyclohexane diisocyanates, 1,3-, 1,4- and1,5-tetrahydronaphthalene diisocyanates, and isophorone diisocyanate(“IPDI,” i.e.,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane); monomericunsaturated triisocyanates such as 2,4,4′-diphenylene triisocyanate,2,4,4′-diphenylmethane triisocyanate, and 4,4′,4″-triphenylmethanetriisocyanate; monomeric saturated triisocyanates such as1,3,5-cyclohexane triisocyanate, triisocyanate of HDI, and triisocyanateof TMDI; dimerized uretdiones of unsaturated polyisocyanates such asuretdione of toluene diisocyanates, and uretdione of diphenylmethanediisocyanates; dimerized uretdiones of saturated polyisocyanates such asuretdione of hexamethylene diisocyanates; trimerized isocyanurates ofunsaturated polyisocyanates such as trimer of diphenylmethanediisocyanate, trimer of tetramethylxylene diisocyanate, and isocyanurateof toluene diisocyanates; and trimerized isocyanurates of saturatedpolyisocyanates such as isocyanurate of isophorone diisocyanate,isocyanurate of hexamethylene diisocyanate, and isocyanurate oftrimethyl-hexamethylene diisocyanates.

The following polyisocyanates are also useful for the presentdisclosure: perchlorinated, monochlorinated and unchlorinated aromaticdiisocyanates and triisocyanates (such as are disclosed in U.S. Pat. No.3,277,138); isocyanates derivable by dehydration and rearrangement of1-amino-cyclohexanecarbohydroxamic acid hydrohalides (such as aredisclosed in U.S. Pat. No. 3,703,542); diisocyanato-urethanes (such asare described in U.S. Pat. No. 3,813,380); polymethylene diisocyanates(such as are described in U.S. Pat. Nos. 2,394,597, 3,465,024 and3,840,572); isocyanates derivable by heating the cyclic nitrile sulfitesof U.S. Pat. No. 3,268,542 (e.g., 3-hydroxy- or 3-nitro-1,4-diisocyanatobenzene, 4-bromo-1,3,5-triisocyanato benzene and 2,2′-stilbenediisocyanate); ethylenically-unsaturated diisocyanates derivable byheating the cyclic nitrile sulfites of U.S. Pat. No. 3,560,492 (e.g.,transvinylenediisocyanate); isocyanate-functional polymers derivable byheating the homo- and copolymers of ethylenically unsaturated cyclicnitrile carbonates and oxalates (such as are disclosed in U.S. Pat. Nos.3,480,595, 3,652,507 and 3,813,365, e.g., the thermoplasticpolyisocyanate formed upon heating a copolymer of styrene andp-vinylbenzonitrile carbonate and/or acrylonitrile carbonate);heteroaliphatic and heterocyclic isocyanates derivable from aminecompounds in which acyclic and cyclic hydrocarbyl moieties areinterrupted by or linked through —O—, —S—, —N(R)—, —N═, or otherheteroatoms (non-limiting examples including β-ethoxy-N-amylamine,β-phenoxyethylamine, β-methylthio-ethylamine, di-α-aminopropyl)-ether,3-amino-diphenylether, di-(β-aminoethyl)-sulfide,ethyl-3-aminophenylsulfide, 2-aminothiophene, 1-furyl-2-aminopropane,2-thenylamine, 2,4-diamino-5-phenylthiazole, 3,5-diaminopyridine, and2,4′-diamino-diphenylsulfide); isocyanates derivable frompolyaminehydrocarbons (such as are prepared by ammonolysis ofchlorinated polyolefins under pressure in polar solvents such as ethanolor dimethylformamide); and isocyanates derivable from acetate esters ofmono- and poly-hydroxamic acids or from dihydroxamic acids and theirmetal salts (the processes of which are disclosed in U.S. Pat. Nos.3,465,024 and 2,394,597, respectively). The process of preparingisocyanates by heating cyclic nitrile carbonates is disclosed in detailin U.S. Pat. No. 3,507,900. A process for making difunctional cyclicnitrile carbonates by the reaction of dihydroxamic acids and phosgene isdisclosed in U.S. Pat. No. 3,825,554. Isocyanates can be converted fromthe polyamines and polyamine telechelics disclosed herein by knownmethods such as those found in Synthetic Organic Chemistry (1953),Wagner and Zook, Wiley, N.Y., N.Y., pp. 460-1.

Other suitable polyisocyanates include, for example, polymericpolyisocyanates and modified polyisocyanates (i.e., polyisocyanatescontaining carbodiimide groups, urethane groups, allophanate groups,isocyanurate groups, urea groups, biuret groups, or other groups knownto one skilled in the art), such as, without limitation, polyphenylenepolymethylene polyisocyanate (“PMDI,” i.e., polymeric MDI, orpolyphenyl-polymethylene polyisocyanates, as are obtained byaniline-formaldehyde condensation and subsequent phosgenation anddescribed, for example, in GB-874430 and GB-848671), m- andp-isocyanatophenylsulfonyl isocyanates according to U.S. Pat. No.3,454,606, perchlorinated aryl polyisocyanates (as are described in U.S.Pat. No. 3,277,138), polyisocyanates containing carbodiimide groups (asare described in U.S. Pat. Nos. 3,152,162, 4,077,989, 4,088,665,4,294,719, and 4,344,855, such as carbodiimide-modified liquid MDI),norbornane diisocyanates according to U.S. Pat. No. 3,492,301,polyisocyanates containing allophanate groups (as are described inGB-994890, and in U.S. Pat. Nos. 3,832,311 and 3,769,318),polyisocyanates containing isocyanurate groups (as are described inGB-843841, GB-1091949, GB-1267011, and U.S. Pat. No. 3,738,947),polyisocyanates containing urethane groups (as are described, forexample, in GB-1303201 and in U.S. Pat. Nos. 3,394,164 and 3,644,457),polyisocyanates containing acylated urea groups according to U.S. Pat.No. 3,517,039, polyisocyanates containing biuret groups (as aredescribed in U.S. Pat. Nos. 3,124,605 and 3,201,372, and in GB-889050),polyisocyanates prepared by telomerisation reactions (as are describedin U.S. Pat. No. 3,654,106), polyisocyanates containing ester groups (asare mentioned in GB-965474, GB-1072956, GB-1086404, and in U.S. Pat. No.3,567,763), reaction products of the above-mentioned isocyanates withacetals according to U.S. Pat. No. 3,120,502, and polyisocyanatescontaining polymeric fatty acid esters according to U.S. Pat. No.3,455,883. These disclosures are incorporated by reference herein. It ispossible to use the distillation residues containing isocyanate groupsthat are formed in the commercial preparation of isocyanates, optionallydissolved in one or more of the above-mentioned polyisocyanates. It isalso possible to use any desired mixtures of the above-mentionedpolyisocyanates and isomers thereof.

One or more or all of the reactable isocyanate groups within thepolyisocyanate compound can be sterically hindered, so that thepolyisocyanate compound provide the combination of reduced reactivitytoward active hydrogen groups such as primary and secondary amines, andimproved chemical stability toward actinic radiations such as UV light.Sterically hindered NCO group can have the following structure:

where C₁, C₂, and C₃ are independent tertiary (i.e., methine) orquaternary carbon atoms. One, two, or all three of C₁, C₂, and C₃ can befree of C—H bonds. C₁, C₂, and C₃ may in part form a substituted ringstructure having about 4-30 carbon atoms. The ring structure may besaturated, unsaturated, aromatic, monocyclic, polycyclic (e.g.,bicyclic, tricyclic, etc.), or heterocyclic having one or more O, N, orS atoms. The ring structure may have one, two, three, or more moietiesof the structure (8), while the polyisocyanate compound may have one,two, or more of such ring structures. For example, the polyisocyanatemay have a structure of:

where Z₁ to Z₈ are independently chosen from halogenated orunhalogenated hydrocarbon moieties having about 1-20 carbon atoms,halogenated or unhalogenated organic moieties having at least one O, N,S, or Si atom and zero to about 12 carbon atoms, and halogens; Y₁ to Y₄are independently chosen from hydrogen, halogenated or unhalogenatedhydrocarbon moieties having about 1-20 carbon atoms, halogenated orunhalogenated organic moieties having at least one O, N, S, or Si atomand zero to about 12 carbon atoms, and halogens; Z is halogenated orunhalogenated hydrocarbon moieties having about 1-60 carbon atoms, orhalogenated or unhalogenated organic moieties having at least one O, N,S, or Si atom and zero to about 60 carbon atoms. Z can have one of thestructures (41)-(48) above. Other examples of sterically hinderedpolyisocyanates include, without limitation, 1,4-durene diisocyanate(“DDI,” i.e., 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene) and2,3,5,6-tetramethyl-1,4-diisocyanatocyclohexane. Elastomer compositionscomprising DDI as described in U.S. Publication No. 2003/0135008 areincorporated herein by reference.

The polyisocyanate can have NCO groups of different reactivity, i.e.,being regioselective. Reactants having high regioselectivity in generalcan enable efficient use in consecutive reactions such as polymerizationsteps and crosslinking. They can provide cost advantages by reducingwaste of functional groups (i.e., reduction in unreacted reactants),provide handling advantages by reducing volatile “leftover” molecules,and provide performance advantages by enabling controlled architecturein the reaction products (e.g., reduced polydispersity). Regioselectivepolyisocyanates can be asymmetric in structure, having at least twosterically different NCO groups, one being more sterically interferedthan the other. The more sterically interfered NCO group can be directlyattached to a tertiary carbon atom, or be one methine carbon atom awayfrom either a quaternary carbon atom or two tertiary carbon atoms. Theless sterically interfered NCO group can be at least two carbon atomsaway from either a quaternary carbon atom or two tertiary carbon atoms,and can be attached directly to a methylene carbon or a methine carbon.Regioselective polyisocyanates can have a structure of:

where R₁, R₂, and R₄ are independent organic moieties having about 1-20carbon atoms, such as linear or branched aliphatic hydrocarbon moietieshaving about 1-12 carbon atoms, like C₁ to C₈ alkyl groups; R₃ isorganic moieties having about 2-20 carbon atoms, such as linear orbranched aliphatic hydrocarbon moieties having about 2-12 carbon atoms,like C₂ to C₁₀ alkylene moiety; R₅ and R₆ are the same or differentorganic moieties having about 1-20 carbon atoms, such as linear orbranched aliphatic hydrocarbon moieties having about 1-8 carbon atoms,like C₁ to C₄ alkylene moieties; R₇ is organic moieties having zero toabout 20 carbon atoms, such as hydrogen or linear or branched aliphatichydrocarbon moieties having about 1-12 carbon atoms, like C₁ to C₈ alkylgroups; R₈ is organic moieties having about 1-20 carbon atoms, such aslinear or branched aliphatic hydrocarbon moieties having about 1-12carbon atoms, like C₁ to C₈ alkylene moiety; and x, y, and z areindependently 0 or 1. The regioselective polyisocyanates can besaturated aliphatic or alicyclic. Non-limiting examples include1,4-diisocyanato-4-methylpentane, 1,5-diisocyanato-5-methylhexane,1,6-diisocyanato-6-methylheptane,1,5-diisocyanato-2,2,5-trimethylhexane,1,7-diisocyanato-3,7-dimethyloctane,3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate (which is generallypresent as a mixture of the 3- and 4-isocyanatomethyl isomers),3(4)-isocyanatomethyl-1-1,3(4)-dimethylcyclohexane isocyanate (which isgenerally present as a mixture of the 3-methyl-3-isocyanatomethyl and4-methyl-4-isocyanatomethyl isomers),3-isocyanatomethyl-1,2-dimethyl-3-ethyl-cyclopentane isocyanate,3-(2-isocyanatoethyl)-1,2,2-trimethylcyclopentane isocyanate,4-(4-isocyanatobut-2-yl)-1-methylcyclohexyl isocyanate, and3-(4-isocyanatobut-1-yl)-1-n-butyl-cyclohexane isocyanate.

In certain polyisocyanates, the NCO groups initially have about the samereactivity, but the reaction of a first NCO group with an activehydrogen functionality can induce a decrease in the reactivity of asecond NCO group. Non-limiting examples of such polyisocyanates includepolyisocyanates whose NCO groups are coupled via a delocalized electronsystem, such as tolidine diisocyanate, tolylene 2,4-diisocyanate(2,4-TDI), tolylene 2,6-diisocyanate (2,6-TDI),diphenylmethane-2,4′-diisocyanate (2,4′-MDI), phenylene-1,3- and1,4-diisocyanate, naphthylene-1,5-diisocyanate, triisocyanatotoluene,and biphenyl diisocyanate.

Other polyisocyanates include1,7-diisocyanato-4-isocyanatomethylheptane,1,8-diisocyanato-4-isocyanatomethyloctane, 2-butyl-2-ethylpentamethylenediisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, isophoronediisocyanate (IPDI), 4-methylcyclohexane-1,3-diisocyanate (HTDI),dicyclohexylmethane-2,4′-diisocyanate, and those disclosed in U.S. Pat.No. 4,808,691, column 12, line 17 to column 13, line 39, which areincorporate herein by reference.

Polyisocyanates can be derived from the fatty polyacids of the presentdisclosure. The fatty polyisocyanates can have the same hydrocarbonstructures as the fatty polyacids, except that each COOH group isreplaced by an NCO group. For example, dimer diacids can be used to formsaturated and/or unsaturated dimer diisocyanates. Dimer diisocyanatesmay be linear, branched (such as with linear or branched alkyl groups),cyclic, and/or substituted, and can be unsaturated, partly hydrogenated,or completely hydrogenated (i.e., fully saturated). Non-limiting dimerdiisocyanates can have one of the following structures:

where R is the same or different moieties chosen from hydrogen, alkyl,aryl, aralkyl, alicyclic, cycloalkyl, and alkoxy groups; x+y and m+n areboth at least about 8, such as at least about 10, such as 12, 14, 15,16, 18, 19, or greater.

Fatty polyisocyanates can have at least one divalent hydrocarbon radicalhaving at least 30 carbon atoms, such as 36-180 carbon atoms, which canbe linear, branched, cyclic, and/or substituted, such asmonocycloaliphatic moiety having a 6-membered carbon ring (e.g.,cyclohexene ring), bicycloaliphatic moiety having a 10-membered carbonring, and substituted aliphatic moiety (e.g., halogenated aliphaticmoiety such as fluoroaliphatic polyisocyanates). Fatty polyisocyanatessuch as dimer diisocyanates are water insensitive, have controllablereactivity and low toxicity when compared to other aliphaticpolyisocyanates. The fatty polyisocyanates can have a % NCO content of20% or less, 15% or less, 10% or less, 5% or greater, or any amountstherebetween, such as 6-9%, 12-16%, 13-15%, or 13.6-14.3%. The fattypolyisocyanates can have a molecular weight of 250 or greater, such as500 or greater or 600 or greater, and up to about 15,000, such as about500-10,000. Fatty polyisocyanates can be liquid at room temperature,having low to moderate viscosity at 25° C. (e.g., about 100-10,000 cP orabout 500-5,000 cP). Other dimer diisocyanates are described in, forexample, Kirk-Othmer Encyclopedia of Chemical Technology 1979, volume 7,3^(rd) edition, p. 768-782, John Wiley and Sons, Inc., the disclosure ofwhich is entirely incorporated herein by reference.

Curatives

Any and all of the compounds having two or more isocyanate-reactivefunctionalities as disclosed herein may be used as curatives to cureprepolymers into thermoplastic or thermoset compositions. Thesecuratives can be polyamines, polyols, aminoalcohols, polyaminetelechelics, and polyol telechelics, and aminoalcohol telechelics. Tofurther improve the shear resistance of the resulting elastomers,trifunctional curatives, tetrafunctional curatives, and higherfunctionality curatives can be used to increase crosslink density. Othercuratives include those disclosed in U.S. Pat. No. 4,808,691, fromcolumn 9, line 24 to column 12, line 16, in U.S. Pat. No. 5,484,870,from column 2, line 47 to column 3, line 41, which are incorporatedherein by reference.

The curative can be a modified curative blend as disclosed in co-pendingU.S. Patent Publication No. 2003/0212240, bearing Ser. No. 10/339,603,which is incorporated by reference herein in its entirety. For example,the curative may be modified with a freezing point depressing agent tocreate a curative blend having a slow onset of solidification andstorage-stable pigment dispersion. A number of curatives have relativelyhigh freezing points, e.g., hexamethylene diamine (105.8° F.),diethanolamine (82.4° F.), triethanolamine (69.8° F.),diisopropanolamine (73.4° F.), and triisopropanolamine (111.2° F.). Suchcuratives may be blended with one or more amine-based freezing pointdepressing agents such as, without limitation, ethylene diamine,1,3-diaminopropane, dimethylaminopropylamine, tetraethylene pentamine,1,2-propylenediamine, diethylaminopropylamine,2,2,4-trimethyl-1,6-hexanediamine, and2,4,4-trimethyl-1,6-hexanediamine.

The freezing point depressing agent can be added in an amount sufficientto reduce the freezing point of the curative blend by a suitable amountto prevent loss of pigment dispersion, but not adversely affect thephysical properties of the resulting golf ball, such as about 5% byweight or greater of the total blend, about 8%, about 10%, about 12%,about 14%, or any amount therebetween or even greater. After freezingand subsequent thawing, the modified curative blend can have a pigmentdispersion of greater than 0 on the Hegman scale, such as about 1, about2, about 3, about 4, about 5, about 6, about 7, or some leveltherebetween or even greater.

Curatives comprising one or more ethylenic and/or acetylenicunsaturation moieties can be used to incorporate these moieties into theresulting material for subsequent crosslinking, as described hereinbelow. Such unsaturated moieties include allyl groups andα,β-ethylenically unsaturated C₃ to C₈ carboxylate groups. Non-limitingexamples of curatives comprising allyl groups include trimethylolpropanemonoallyl ether, N-methylolacrylamide, glyceryl-α-allyl ether,1,1-dihydroxymethylcyclohex-3-ene, 1,2-dihydroxymethylcyclohex-4-ene,and the like. Curatives comprising (meth)acryloyl groups include estersof (meth)acrylic acids with diols or polyols. Non-limiting examplesinclude 2-hydroxyethyl, 2- or 3-hydroxypropyl or 2-, 3- or4-hydroxybutyl (meth)acrylates and mixtures thereof. Monools comprising(meth)acryloyl groups or reaction products substantially composed ofsuch alcohols that are obtained by esterification of n-hydric alcoholswith (meth)acrylic acid are suitable. Mixtures of various alcohols canbe used, such that n stands for an integer or a statistical average ofgreater than about 2 to about 10, preferably about 2 to about 4, andmore preferably about 3. Per mole of the polyols mentioned, (n−0.6) to(n−2.2), (n−0.8) to (n−1.2), or (n−1) moles of (meth)acrylic acids canbe used. These compounds or product mixtures include the reactionproducts of:

(i) triols such as glycerol, trimethylolpropane and/or pentaerythritol;low-molecular-weight alkoxylation products of such alcohols (e.g.,ethoxylated or propoxylated trimethylolpropane more specifically theaddition product of ethylene oxide to trimethylolpropane having an OHnumber of 550); or mixtures of at least triols with diols (e.g.,ethylene glycol or propylene glycol), and

(ii) (meth)acrylic acid in the stated molar ratio. Said compounds have amolecular weight of 116 to 1000, such as 116 to 750 or 116 to 158.

Furthermore, the reaction products of said monols comprising(meth)acryloyl groups with, for example, ε-caprolactone can also beused. Such products can be obtained, for example, as Tone® M-100, M-101,and M-201 monomers from Dow Chemical. These compounds have a molecularweight of 230 to 3000, such as 230 to 1206 or 344 to 572.

(Meth)acryloyl alcohols also include urethane (meth)acrylates thatcontain (meth)acryloyl groups and free hydroxyl groups, such as reactionproducts of urethane (meth)acrylates with diols, optionally mixed withpolyols. Aliphatic, cycloaliphatic and/or aromatic diols can be used asdiols, for example ethylene glycol, the isomeric propanediols,butanediols, pentanediols, hexanediols, heptanediols, octanediols,nonanediols and cyclohexanedimethanol, hydrogenated bisphenol-A andderivatives of the above mentioned diols substituted with one or moreC₁-C₆-alkyl groups. Also suitable are diols containing ester groups,ether groups such as(3-hydroxy-2,2-dimethylpropyl)-3-hydroxy-2,2-dimethylpropionate ordiethylene glycol, dipropylene glycol, and tripropylene glycol.Non-limiting examples are neopentyl glycol,2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol,2,5-dimethyl-1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and3-hydroxy-2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropionate. The diolsmay also be used in the form of their alkoxylation products (ethyleneoxide, propylene oxide, and C₄-ether units). The use of polyester diolsis also possible. These include the reaction products of dicarboxylicacids and/or their anhydrides, ethylenically unsaturated dicarboxylicacids and/or their anhydrides, and lactones (such as ε-caprolactone)with the above mentioned diols. Also suitable iscc,co-dihydroxypolyacrylates (for example, Tegomer® BD 1000 fromGoldschmidt).

Polyurea Compositions

The compositions of the disclosure may comprise at least one polyureaformed from the well-known one-shot method or prepolymer method. In thelatter, polyamine telechelic is reacted with excess polyisocyanate toform polyurea prepolymer, which is then reacted with curative to formthe polyurea. Prepolymer to curative ratio can be as high as 1:0.9 or1:0.95, such as when primary polyamine curatives are used, or as low as1:1.1 or 1:1.05, such as 1:1.02, such as when secondary polyaminecuratives are used. Curative includes polyamines, polyols, polyacids,aminoalcohols, aminoacids, and hydroxy acids, especially those disclosedherein, as well as epoxy-functional reactants, thio-containingreactants, and any other isocyanate-reactive compounds and materials.The polyurea composition can be castable, thermoplastic, thermoset, ormillable.

The content of reactable isocyanate moieties in the polyurea prepolymer,expressed as % NCO by weight, can be manipulated to control such factorsas curing rate, hardness of the resulting material, and the like. Allelse being the same, the hardness of the resulting material can increaseas the % NCO of the prepolymer increases, and can be greater inpolyamine cured compositions than in polyol cured compositions. Thepolyurea prepolymer can be low-melting (such as being fluid at about125° C.) or fluid at ambient temperature. The % NCO by weight in theprepolymer can be less than about 30%, such as about 15%, about 11%,about 9%, about 7%, or even less, or at least about 2%, such as about 3%or about 4% or greater, or any percentage therebetween, such as about5-11%, about 6-9.5%, about 3-9%, about 2.5-7.5%, or about 4-6.8%.

In forming the polyurea prepolymer, polyamine telechelics as disclosedherein can be used alone or in combination of two or more thereof toreact with excess isocyanate. Prepolymers with higher % NCO (e.g., 14%)can be converted to prepolymers with lower % NCO (e.g., 10%) by furtherreacting with one or more other polyamines, polyols, polyaminetelechelics, and/or polyol telechelics (e.g., polyamine polyamides,polyol polysiloxanes). The polyamine telechelic can have one amidelinkage, two amide linkages, one or more segments having multiple amidelinkages, or a polyamide backbone. When a plurality of amide linkages ispresent, one or more of them can conjoin consecutive repeating units oralternating repeating units. Polyurea prepolymers may contain a contentof free isocyanate monomers by about 10% and up to about 20% of thetotal weight, which can be stripped down to about 1% or less, such asabout 0.5% or less.

When forming a saturated prepolymer, such as for use in highlylight-stable compositions, saturated polyisocyanates being aliphatic,alicyclic, and/or heteroaliphatic can be used alone or in combinationsof two or more thereof. Araliphatic polyisocyanates, alone or inmixtures of two or more thereof, may also be used to form relativelylight-stable materials. Without being bound to any particular theory, itis believed that the direct attachment of the NCO moieties to aliphaticside chains without conjugation with the aromatic rings prevents thearaliphatic polyisocyanates from, or diminishes their ability in,forming extended conjugated double bonds, which may give rise todiscoloration (e.g., yellowing). The sterically hindered polyisocyanatesare useful in forming highly or relatively light-stable materials.Without being bound to any particular theory, it is believed that thesteric hinderance around the N atom tends to rotate it out of plane,thereby reducing its absorbance of UV wavelengths and achieving desiredlight-stability. Moreover, one or more of the NCO groups in thesterically hindered polyisocyanates can be attached to tertiary orquaternary carbon atoms that are substantially free of C—H bonds, thuseliminating or reducing the occurrence of UV-induced oxidation at thecarbon atoms, and in turn slowing degradation or discoloration. Thesaturated polyisocyanates, the araliphatic polyisocyanates, and thesterically hindered polyisocyanates may be used alone or in anycombinations of two or more thereof.

Polyurethane Compositions

The compositions of the disclosure may comprise at least onepolyurethane, such as the reaction product of at least one polyurethaneprepolymer and at least one curative, of which the polyurethaneprepolymer is the reaction product of at least one polyol telechelic andat least one polyisocyanate. Prepolymer to curative ratio can be 1:0.9to 1:1.1, such as 1:0.95, 1:1.05, or 1:1.02. One or more of the polyoltelechelic, the polyisocyanate, and the curative can be chosen fromthose disclosed herein, can be saturated, and the resulting polyurethanecan be saturated. Polyurethane prepolymers can have free isocyanatemonomers by about 10% and up to about 20% of the total weight, which canbe stripped down to about 1% or less, such as about 0.5% or less.

The polyurethane composition can be castable, thermoplastic, thermoset,or millable. The % NCO by weight in the prepolymer can be less thanabout 30%, such as about 15%, about 11%, about 9%, about 7%, or evenless, or at least about 2%, such as about 3% or about 4% or greater, orany percentage therebetween, such as about 5-11%, about 6-9.5%, about3-9%, about 2.5-7.5%, or about 4-6.8%. In forming the polyurethaneprepolymer, polyol telechelics as disclosed herein can be used alone orin combination of two or more thereof to react with excess isocyanate.Prepolymers with higher % NCO (e.g., 14%) can be converted toprepolymers with lower % NCO (e.g., 10%) by further reacting with one ormore other polyamines, polyols, polyamine telechelics, and/or polyoltelechelics (e.g., polyamine polyamides, polyol polysiloxanes). Thepolyol telechelic can have one or two amide linkages, one or moresegments having multiple amide linkages, or a polyamide backbone. When aplurality of amide linkages is present, one or more of them can conjoinconsecutive repeating units or alternating repeating units.

Crosslinkable polyurethanes can be formed from polyol telechelics,curatives, and stoichiometrically deficient amounts of polyisocyanatesuch as diisocyanate. Any one or more the reactants can have one or morealiphatic, non-benzenoid >C══C< moieties for crosslinking. Suchpolyurethanes can have rubber elasticity and wear resistance andstrength, and can be millable. Polyol telechelics of lowcrystallizability, such as those having linear or branched side chainsand those formed by random copolymerization (e.g, polyol polyethers,polyol polyesters, polyol polyetheresters, and others as disclosedherein), can be used to form such polyurethanes. Non-limiting examplesinclude polyethylene propylene adipate polyols, polyethylene butyleneadipate polyols, polytetramethylene ether glycols (such as those havingM_(w) of about 2,000), tetrahydrofuran (THF)-alkyl glycidyl ether randomcopolymers, and other polyol polyesters based on adipic acid and diolslike ethanediol, butanediol, methylpropanediol, hexanediol. Polyoltelechelics can be incorporated with ethylenic and/or acetylenicunsaturation moieties as disclosed above, such as by reacting them withα,β-ethylenically unsaturated carboxylic acids, and then crosslinkedusing vulcanizing agents as disclose herein. Alternatively, thepolyurethanes are substantially free of ethylenic

Formulations comprising such polyurethane materials and optionaladditives such as vulcanizing agents, fillers, plasticizers, lightstabilizers, and others as disclosed herein, can form golf ball portionssuch as cover layers by extrusion, transfer molding, compressionmolding, and/or injection molding. Hemispherical cup can be preformed,such as by compression molding at ambient temperature. The cup halvescan then be compression molded over subassemblies such as cores intoinner cover layer or dimpled outer cover layer at elevated temperature(e.g., 320° F.) and under increased pressure (e.g., 800 psi), duringwhich the formulation is crosslinked. After a period of time (e.g., 2.5minutes) the molds are cooled (e.g., 10 minutes with tap water or 1minute with tap water and then 4 minutes with chilled water) and themolded objects are released from the molds.

Properties of crosslinkable polyurethanes include Mooney viscosity at100° C. of 40-70 (e.g., 50, 60, 65, or therebetween), tensile strengthof 2,000-6,000 psi (e.g., 3,000 psi, 4,000 psi, 5,000 psi, ortherebetween), tear strength of 300-600 lb/in (e.g., 400 lb/in, 500,lb/in, or therebetween), brittle point of −70° F. or lower (e.g., −80°F., −90° F., or lower), material hardness of 25 Shore A to 60 Shore D(e.g., 55 Shore D), elongation at break of 100-700% (e.g., 300%, 400%,500%, 600%, or therebetween), Bashore rebound of 40-70% (45%, 55%, ortherebetween), and abrasion index (ASTM D-1630) of 300 or greater. Othercrosslinkable compositions and components thereof are disclosed in U.S.Pat. Nos. 6,103,852 and 6,008,312, and in U.S. Publication No.2002/0115813, which are incorporated herein by reference.

Poly(urethane-co-urea) Compositions

The compositions of the disclosure may comprise at least onepoly(urethane-co-urea) formed from poly(urethane-co-urea) prepolymer andcurative. Prepolymer to curative ratio can be as high as 1:0.9 or1:0.95, such as when primary polyamine curatives are used, or as low as1:1.1 or 1:1.05, such as 1:1.02, such as when secondary polyaminecuratives are used. Curative includes polyamines, polyols, polyacids,aminoalcohols, aminoacids, and hydroxy acids, especially those disclosedherein, as well as epoxy-functional reactants, thio-containingreactants, and any other isocyanate-reactive compounds and materials.

Poly(urethane-co-urea) prepolymer refers to isocyanate-functionalprepolymer having at least one urethane linkage and at least one urealinkage in the backbone. Such a prepolymer is distinct from polyurethaneprepolymer, polyurea prepolymer, and blends thereof. Thepoly(urethane-co-urea) prepolymer can be formed by reacting excessisocyanate with a blend of at least one polyamine telechelic and atleast one polyol telechelic. Molar ratio of polyol telechelic topolyamine telechelic in the blend can be about 0.5:1 to about 10:1, suchas about 0.6:1 to about 7:1. Examples of blend include polyether polyolssuch as polyoxytetramethylene diol and polyether polyamines such aspolyoxypropylene diamine.

The poly(urethane-co-urea) composition can be castable, thermoplastic,thermoset, or millable. The % NCO by weight in the prepolymer can beless than about 30%, such as about 15%, about 11%, about 9%, about 7%,or even less, or at least about 2%, such as about 3% or about 4% orgreater, or any percentage therebetween, such as about 5-11%, about6-9.5%, about 3-9%, about 2.5-7.5%, or about 4-6.8%. Prepolymers withhigher % NCO (e.g., 14%) can be converted to prepolymers with lower %NCO (e.g., 10%) by further reacting with one or more other polyamines,polyols, polyamine telechelics, and/or polyol telechelics (e.g.,polyamine polyamides, polyol polysiloxanes).

The poly(urethane-co-urea) prepolymer can be formed by reacting excessisocyanate with an aminoalcohol telechelic (or a blend of two or morethereof), optionally mixed with at least one polyamine reactant and/orat least one polyol reactant. The poly(urethane-co-urea) prepolymer canalso be formed by reacting excess isocyanate with a polyamine reactanthaving at least one urethane linkage in the backbone, or with a polyolreactant having at least one urea linkage in the backbone. Polyaminereactants include any one or more polyamine telechelics and polyaminesdisclosed herein. Polyol reactants include any one or more polyoltelechelics and polyols disclosed herein. The poly(urethane-co-urea)prepolymer can further be formed in situ from a mixture of at least onepolyisocyanate, at least one cyclic compound such as cyclic ether, andat least one telechelic chosen from polyamine telechelics, polyoltelechelics, and aminoalcohol telechelics as disclosed herein.

Acid-Functionalized and Ionomerized Compositions

The reactive compositions of the present disclosure can be covalentlyincorporated or functionalized with ionic groups or precursor groupsthereof, which can impart desirable properties to the resulting polymermaterials. The term “ionic group or precursor group thereof” means agroup either already in an anionic or cationic form or else, byneutralization with a reagent, readily converted to the anionic orcationic form respectively. The term “neutralize” as used herein forconverting precursor groups to ionic groups refers not only toneutralization using true acids and bases but also includesquatemarization and ternarization. Illustrative of precursor anionicgroups (and neutralized form) are acid groups like carboxylic group—COOH(—COO^(⊖)), sulfonic group —SO₂OH(—SO₂O^(⊖)), and phosphoric group(i.e., ══POOH or ══POO^(⊖)); illustrative of precursor cationic groups(and neutralized form) are ══N(══N—^(⊕)), ══P(══P—^(⊕)), and══S(══S—^(⊕)).

Without being bound to any particular theory, it is believed that acidfunctional moieties or groups can improve adhesion of the resultingmaterial to other components or layers in the golf ball, while strongelectrostatic interactions among cationic and/or anionic groups formionic aggregates, which may afford desired mechanical and opticalproperties such as cut and abrasion resistance and transparency. Morethan one type of ionic group or precursor group thereof may beincorporated into the reactive composition of the present disclosure.Acid and/or ionic functionalization of the reactive compositions isdisclosed, for example, in U.S. Pat. Nos. 6,610,812, 6,207,784,6,103,822, and 5,661,207.

The precursor groups of ionic groups can be incorporated into theisocyanate-reactive telechelic (including polyamine telechelics, polyoltelechelics, and aminoalcohol telechelics), the isocyanate, and/or thecurative before, during, or after the prepolymer formation or the curingreaction. They can be neutralized to corresponding ionic groups before,during, or after the prepolymer formation or the curing reaction. Forexample, the acid groups may be neutralized to form the correspondingcarboxylate anion, sulfonate anion, and phosphate anion by treatmentwith inorganic or organic bases. Cationic precursor groups such astertiary amine, phosphine, and sulfide groups can be neutralized byneutralization or quatemarization of the tertiary amine, or reacting thephosphine or sulfide with compounds capable of alkylating the phosphineor sulfide groups.

Suitable inorganic bases used for partial or total neutralization mayinclude ammonia, oxides, hydroxides, carbonates, bicarbonates andacetates. Cation for the inorganic base can be ammonium or metal cationssuch as, without limitation, Group IA, IB, IIA, IIB, IIIA, IIIB, IVA,IVB, VA, VB, VIIA, VIIB, VIIB and VIIIB metal ions, which include,without limitation, lithium, sodium, potassium, magnesium, zinc,calcium, cobalt, nickel, tin, iron, copper, manganese, aluminum,tungsten, zirconium, titanium and hafnium. Suitable organic bases usedfor partial or full neutralization can be hindered organic tertiaryamines such as tributylamine, triethylamine, tripropylamine, triethylenediamine, dimethyl cetylamine and similar compounds. Primary or secondaryamines may be used, such as if the neutralization takes place after thepolymer is formed, because the amine hydrogen can react with theisocyanate groups thereby interfering with the polyurea or polyurethanepolymerization. One of ordinary skill in the art is aware of additionalappropriate chemicals for neutralization.

At least a portion of the ionic groups can be covalently incorporatedinto the isocyanate-reactive telechelic before prepolymer formation.Suitable acid functional isocyanate-reactive telechelics may have anymolecular weight, such as 1,500, an acid number (calculated by dividingacid equivalent weight to 56,100) of at least about 5, such as at leastabout 10, at least about 25, at least about 30, or at least about 50,may be about 420 or less, such as about 200 or less, about 150 or less,about 100 or less, and an acid functionality of greater than 1, such as1.4 or greater. In the case of polyol telechelics, the hydroxyl numberof the polyols may be at least about 10, such as at least about 20, atleast about 50, or at least about 65, may be about 840 or less, such asabout 300 or less, about 200 or less, about 150 or less. The polyoltelechelics may also have a hydroxyl functionality (average number ofhydroxyl groups per polyol molecule) of greater than 1, about 2 orgreater, like 1.8, and up to about 4. The acid functional telechelic canbe liquid or wax at ambient temperature, and can have a viscosity at 60°C. of less than 5,000 cP, or 3,000 cP or less, such as 2,700 cP or less.

Ionic groups or precursor groups thereof may be incorporated into themonomers comprised in the telechelic. Monomers containing one or moreionic groups or precursor groups thereof can be, but are not limited to,cyclic ethers or diol monomers used to form polyether chains orsegments, cyclic esters, diol monomers or polycarboxylic acids (such aslithium neutralized sulfonated isophthalic acid, tricarboxylic acids, orhigher acids) used to form polyester chains or segments, cyclic amides,diamine monomers or polycarboxylic acids used to form polyamide chainsor segments, cyclic siloxanes used to form polysiloxane chains orsegments, (meth)acrylic acids used to form poly(meth)acrylic chains orsegments, and fatty polyacids having three or more carboxylic acidfunctionalities and isocyanate-reactive derivatives thereof.Alternatively, the ionic groups or precursor groups thereof may beincorporated into the telechelic via the likes of addition orcondensation reactions between suitable functional groups. For example,unsaturated carboxylic acids such as (meth)acrylic acids and unsaturatedfatty acids as disclosed herein may react with unsaturation in thetelechelic, thereby forming pendant carboxylic acids along thetelechelic chain.

Other methods of incorporating acid groups into the telechelic reactantare disclosed, for example, in U.S. Patent Application No. 2002/0183443,which is incorporated by reference herein in its entirety. For example,dimethylolpropionic acid (DMPA) can provide acid groups by reacting witha starting polyol and a diisocyanate to form an isocyanate-terminatedprepolymer at a temperature that permits the reaction of the hydroxylgroups with excess isocyanate without consuming all of the acid groups.Mono- or polycarboxylic acids or mono- or polyanhydrides (such as thosedisclosed herein, like hexanedioic acid) can provide acid groups byreacting with the starting polyols in the absence of an isocyanate,under reaction conditions that permit the reaction of the anhydride withthe hydroxyl groups of the polyol, but are mild enough to preventfurther reaction of the residual carboxylic acids with hydroxyl groups.Examples of such isocyanate-free acid functional polyol telechelicsinclude Lexorez® 1405-65 and 4505-52, both available from InolexChemical Company of, Philadelphia, Pa. (. These acid functional polyoltelechelic and other polyols as disclosed herein can further react withmono- or polycarboxylic acids or mono- or polyanhydrides (such as thosedisclosed herein, like aromatic anhydrides such as trimelliticanhydride, pyromellitic dianhydride, and phthalic anhydride, oralicyclic anhydrides such as hexahydrophthalic anhydride and(2,5-dioxotetrahydrol)-3-methyl 3-cyclohexene-1,2 dicarboxylicanhydride) to form additional acid functional polyol telechelics.

At least a portion of the ionic groups can be covalently incorporatedinto the isocyanate before prepolymer formation. Isocyanates having atleast one acid functional group may be formed by reacting a isocyanateand an acid functional group containing compound as described in U.S.Pat. Nos. 4,956,438 and 5,071,578, the disclosures of which areincorporated herein by reference.

The acid groups may also be incorporated during a post-polymerizationreaction, wherein the acid functional groups are introduced or attachedto the polyurea, the polyurethane, or the poly(urethane-co-urea).Moreover, the acid functional polyurea, polyurethane, orpoly(urethane-co-urea) made by ways of copolymerization as describedabove may be further incorporated with additional acid functional groupsthrough such post-polymerization reactions. Suitable agents toincorporate acid functional groups and methods for making are describedat least in U.S. Pat. No. 6,207,784, the disclosure of which isincorporated by reference herein. One of ordinary skill in the art wouldbe aware of other ways to prepare the acid functional polymercomposition. For example, a combination of the means for acidfunctionality incorporation as described above may be used as describedin U.S. Pat. No. 5,661,207, the disclosure of which is incorporated byreference herein.

Composition Additives

Additional materials may be incorporated into any of the reactivecompositions of the present disclosure, or any one or more of thereactive subcomponents thereof. These additives include, but are notlimited to, catalysts to alter the reaction rate, fillers to adjustdensity and/or modulus, processing aids or oils (such as reactive ornon-reactive diluents) to affect rheological and/or mixing properties,reinforcing materials, impact modifiers, wetting agents, viscositymodifiers, release agents, internal and/or external plasticizers,compatibilizing agents, coupling agents, dispersing agents, crosslinkingagents, defoaming agents, surfactants, lubricants, softening agents,coloring agents including pigments and dyes, optical brighteners,whitening agents, UV absorbers, hindered amine light stabilizers,blowing agents, foaming agents, and any other modifying agents known oravailable to one of ordinary skill in the art. One or more of theseadditives are used in amounts sufficient to achieve their respectivepurposes and desired effects. For example, wetting additives may beadded to the modified curative blends of the disclosure to moreeffectively disperse pigments. Suitable wetting agents are availablefrom Byk-Chemle and Crompton Corporation, among others.

a) Catalysts

One or more catalysts may be employed to alter the reaction rate betweenthe prepolymer and the curative for the reactive compositions. Inpolyurethane compositions, positive catalysts (i.e., promoters) aretypically used to speed up the reaction between isocyanate groups andhydroxyl groups. In polyurea compositions, negative catalysts (i.e.,inhibitors) may be used to slow down the typically fast reaction betweenisocyanate groups and amine groups. The same catalyst may be a promoterin a polyurethane system and an inhibitor in a polyurea system. Suitablecatalysts include, but are not limited to, bismuth catalysts; zinccatalysts such as zinc octoate; cobalt catalysts such as cobalt (II)octoate; zirconium catalysts such as zirconium (IV) acetoacetonate andzirconium (IV) acetylacetone-2,4-pentanedione; tin catalysts such asdibutyltin dilaurate (DABCO® T-12), dibutyltin diacetate (DABCO® T-1),dibutyltin maleate, dioctyltin dilaurate, dibutyltin di-2-ethylhexoate,tin(II) ethylhexoate, tin(II) laurate, tin(II) octoate, dibutyltinoxide, tin (II) chloride, tin (IV) chloride, dibutyltin dimethoxide(FASCAT®-4211), dibutyltin dibutoxide (FASCAT® 4214), dioctyltindiisooctylmercaptoacetate (FORMEZ® UL-29), dibutyltindiisooctylmercaptoacetate, dimethyltin diisooctylmercaptoacetate,dibutyltin dilaurylmercaptide, dioctyltin dilaurylmercaptide,dimethyltin dilaurylmercaptide, stannous octoate (DABCO® T-9), butylstannoic acid, dimethyl-bis[1-oxonedecyl)oxy] stannane (FORMEZ® UL-28),and 1,3-diacetoxytetrabutylstannoxane; titanium catalysts such as2-ethylhexyl titanate, tetraisopropyl titanate, tetrabutyl titanate, andtetrakis-2-ethylhexyl titanate; amine catalysts such astriethylenediamine (DABCO® 33-LV), triethylamine, tributylamine, andN-methylmorpholine; organic acids such as acetic acid, adipic acid,azelaic acid, and oleic acid; delayed catalysts such as phenol-blocked1,8-diaza-bicyclo(5,4,0)undecene-7 (Polycat™ SA-1/10), Polycat™ SA-1,Polycat™ SA-2, Polycat™ SA-102, Polycat™ 8154, Polycat™, and the like.These catalysts can be used alone or in combinations of two or morethereof.

Delayed action catalysts can also be used. These catalysts display theircatalytic activity at a later time point in the reaction. They can beheat-activated, when external heating and/or internal heat from theexothermal reaction elevate the temperature of the reaction mixture toor above the activation temperature of the catalyst. One group of thedelayed action catalyst is cyclic amidines, which can have a genericstructure of:

where n=0 or 1; R₁ to R₇ are independently chosen from hydrogen andlinear or branched aliphatic, alicyclic, araliphatic, and aromaticmoieties, such as C₁-C₄ linear or branched alkyl, C₅-C₁₀ cycloalkyl,C₇-C₁₃ aralkyl, and C₆-C₁₈ aryl moieties, or at least one of R₂/R₃,R₄/R₅, R₆/R₇, R₂/R₄ and R₂/R₆ is a C₁-C₅ alkylene moiety; R₈ is chosenfrom hydrogen and linear or branched aliphatic, alicyclic, araliphatic,and aromatic moieties having 1-36 carbon atoms, optionally substitutedby one or more of OH, COOH, OR, NR₉R₁₀, or comprising at least one (upto about 10) of keto, amide, and ester moieties, or—CH(R)—[OCH₂—CH(R)]_(p)—H, where p is 1-40, R is chosen from linear orbranched C₁-C₂₀ alkyl, cycloalkyl, aryl, and aralkyl moieties (e.g.,C₁-C₁₅ alkyl, C₆-C₁₉ aryl), R₉ and R₁₀ are independently chosen fromhydrogen and linear or branched aliphatic, alicyclic, araliphatic, andaromatic moieties (e.g., C₁-C₁₂ linear or branched alkyl, C₆-C₈cycloalkyl) or R₉/R₁₀ is a C₄-C₆ alkylene moiety. Alternatively, thesecyclic amidines can be used as blocking agent to block isocyanatefunctionalities in the prepolymer, allowing the isocyanate-blockedprepolymer to be thoroughly blended with the curative, and thende-blocking the prepolymer to enable the cure. This mechanism can beused in curing of polyurea composition to slow down reaction and extendpotlife. These and other cyclic amidines as disclosed in U.S. Pat. No.4,698,426 are incorporated herein by reference.

The catalyst can be added in an amount sufficient to catalyze thereaction of the components in the reactive mixture, such as about0.001-5% by weight of the composition, about 0.005-1%, about 0.05% orgreater, or about 0.5% or greater. Use of low levels of tin catalysts,such as about 0-0.04%, may require high temperatures to achieve asuitable reaction rate, which can result in degradation of theprepolymer. Greater amounts of catalysts may allow reduction in processtemperatures with comparable cure, and allow reduction in mixing speeds.Unconventionally high amounts of catalysts can be about 0.01-0.55%,about 0.05-0.4%, or about 0.1-0.25%.

Diluents

As used herein, the term “diluent” refers to any compound or compositionthat can reduce viscosity, reduce reaction exotherm, and/or impart orenhance properties such as flame retardancy, processability,compatibility, and moisture resistance, without adversely affecting thequalitative or physical properties of the resulting polymer. Diluentsare distinct from solvents in that diluents remain within the polymerpost-cure, while solvents are evaporated off post-cure. Diluent can belinear or branched, aliphatic, alicyclic, aromatic, or araliphatic,saturated or unsaturated, substituted or unsubstituted, halogenated orhalogen-free, and/or hydrophobic or hydrophilic, and include within itsscope plasticizer materials. Diluents can be reactive or substantiallyunreactive. Diluent can be substantially water insoluble. Diluent can beadded at any time before, during, or after prepolymer preparation, e.g.,separately or as a mixture with one or more reaction components prior toprepolymer preparation, in amount sufficient to reduce the viscosity ofthe prepolymer to about 1,000-4,000 cP at temperatures of about 125° C.or less. Diluents can have a viscosity of about 50 cP or less at 25° C.Diluents can have a boiling point of greater than 90° C.

The diluent can be used individually or in blends of two or morethereof, and can comprise at least about 0.05% by weight of theprepolymer or the total reactive composition, such as 2%, 3%, 4%, 5%,6%, 10%, 15%, 18%, 20%, 35%, 50%, 60%, 70%, or greater or any amounttherebetween. Suitable diluent can be chosen according to parameterssuch as compatibility with the composition and desired properties of thefinal polymer. For example, ester diluents tend to be compatible withpolyester-based prepolymers. Reactive diluents can react with one ormore functionalities of one or more ingredients in the composition. Forexample, epoxy and carbonate diluents can react with ingredients havingamine groups and/or hydroxyl groups, while ethylenically unsaturateddiluents can react with ingredients having ethylenic unsaturation.

Suitable diluents include those described in U.S. Pat. Nos. 3,773,697,5,929,153, 3,929,700 and 3,936,410, and 4,343,925 (column 9, line 37 tocolumn 13, line 62), the disclosures of which are incorporated herein byreference. Non-limiting examples of diluents include phosphates, esters,epoxies, carbonates, ethers, alkoxylated alcohols, fatty telechelics,such as:

a) cyclic carbonates which can be substituted (with groups such asalkyl, hydroxyalkyl, halogen, etc.) or unsubstituted, and can beprepared such as reacting a compound having an oxirane group (e.g.,cyclic ether such as propylene oxide) with carbon dioxide, having astructure of:

where x is about 1-9, such as 1 or 2; n is 1 to about 40, such as 1, 2,3, or even integers of about 4-20, like 4 or 6; R is the same ordifferent moieties independently chosen from hydrogen, linear orbranched hydrocarbon groups (such as alkyl, aryl, cyclic, saturated, orunsaturated) having about 1-20 carbon atoms, such as about 1-18, about1-6, or about 1-3 carbon atoms, linear or branched hydroxyalkyl groupshaving about 1-20 carbon atoms, such as about 1-18, about 1-6, or about1-3 carbon atoms, linear or branched alkoxyalkylene orpolyalkoxyalkylene, linear or branched haloalkyl groups having about1-20 carbon atoms, such as chloromethyl, linear or branched—C_(m)H_(2m+1) or —C_(m)H_(2m)OH where m is about 1-8, and linear orbranched —(CH₂)_(m)H or —(CH₂)_(m)OH where m is about 1-2, linear orbranched alkoxy groups such as methoxyl and ethoxyl, aryloxy groups suchas phenoxyl, including 5-membered cyclic carbonates such as ethylenecarbonate, propylene carbonate, butylene carbonate, isobutylenecarbonate, styrene carbonate, phenylethylene carbonate, butyl soyatecarbonate, butyl linseed carbonate, and glycerin carbonate, fatty acidcarbonates like oleic acid 8,9-carbonate, succinic acid glycerylcarbonate monoester, glutaric acid glyceryl carbonate monoester,9,10-dihydroxystearic acid carbonate, and 6-membered cyclic carbonatessuch as cyclic trimethylolpropane carbonate and those disclosed in U.S.Pat. Nos. 4,501,905 and 4,440,937, which are incorporated herein byreference, with suitable examples available under the tradename Jeffsol®from Huntsman Corporation, Austin, Tex.;

b) phosphorus-containing compounds including phosphites (e.g., triarylphosphites like triphenyl- and tritolyl phosphite, dialkyl phosphiteslike diisopropyl-, dibutyl-, bis(2-ethylhexyl)-, bis(tridecyl)-, anddioleyl phosphites, trialkyl phosphites like tris(2-ethylhexyl)-,triisopropyl-, tributyl-, tris(2-chloroethyl)-, and triisooctylphosphites, cyclic phosphate esters and cyclic phosphonate esters (e.g.,those disclosed in U.S. Pat. No. 5,030,674, column 3, line 63 to column4, line 55, which is incorporated by reference herein), and phosphateesters (e.g., trialkyl phosphates like triethyl-, tributyl-,tris(2-ethylhexyl)-, tricresyl-, trioctyl-, 2-ethylhexyldiphenylphosphate, isodecyldiphenyl phosphate, cresyldiphenyl phosphate,p-t-butylphenyldiphenyl phosphate, triphenyl phosphate, trixylylphosphate, trixylenyl phosphate, phenyldicresyl phosphate,xylenyldicresyl phosphate, cresyldixylenyl phosphate, tributoxyethylphosphate, chloroalkyldiphosphate esters, trichloroethyl phosphate,and tris(isopropyl)chlorophosphate, chlorinated biphenyl phosphate,chlorinated diphosphate, phosphonates such as chlorinatedpolyphosphonate, alkyloxylated fatty alcohol phosphate esters such asoleth-2 phosphate, oleth-3 phosphate, oleth-4 phosphate, oleth-10phosphate, oleth-20 phosphate, ceteth-8 phosphate, ceteareth-5phosphate, ceteareth-10 phosphate, PPG ceteth-10 phosphate, some ofwhich are available from Albemarle Corporation of Baton Rouge, La.,Great Lakes Chemical Corporation of West Lafayette, Ind., and RhodiaInc. of Cranbury, N.J.;

c) epoxies such as butylepoxy stearate, octylepoxy stearate, epoxybutyloleate, epoxidized butyl oleate, epoxidized soybean oil, epoxidizedlinseed oil, epoxidized alkyl oil, epoxidized alkyl oil alcohol ester,mono-, di-, and polyglycidyl ethers of castor oil and other fattypolyols and fatty polyol telechelics like those disclosed herein, mono-,di-, and polyglycidyl esters of fatty polyacids and dimer acids likethose disclosed herein, such as Heloxy® and Cardura® by ResolutionPerformance Products of Houston, Tex.;

d) alkyl and/or aryl esters, diesters, triesters, dialkyl or diaryldiesters, trialkyl or triaryl triesters of such acids and anhydrides asacetic acid, hexanoic acid, adipic acid, azelaic acid, benzoic acid,citric acid, dimer acids, fumaric acid, isobutyric acid, isophthalicacid, lauric acid, linoleic acid, maleic acid, maleic anhydride,melissic acid, myristic acid, oleic acid, palmitic acid, phthalic acid,ricinoleic acid, sebacic acid, stearic acid, succinic acid,1,2-benzenedicarboxylic acid, and the like, and mixtures thereof, wherethe alkyl group can independently be linear or branched alkyl havingabout 1-20 carbon atoms, H₃CO(CO)(CH₂)_(n)(CO)OCH₃ where n is an integerof about 1-10 or about 8-20, such as methyl 2-ethylhexanoate, butylacetate, methyl laurate, methyl linoleate, isopropyl myristate, butyloleate, methyl palmitate, butyl ricinoleate, methyl stearate, dibenzoateesters, di(aminobenoate) esters, 2-ethylhexylbenzoate, dimethyl adipate,diisopropyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, dicapryladipate, di-n-decyl adipate, and diisodecyl adipate, polypropyleneadipate, heptyl nonyl adipate, dimethyl azelate, dimethyl sebacate,dibutyl sebacate, di-2-ethylhexyl sebacate, dimethyl glutarate, dimethylsuccinate, diethyl succinate, dibutyl fumarate, dioctyl fumarate,di-n-butyl maleate, butyl octyl phthalate, butylcyclohexyl phthalate,butyllauryl phthalate, butylcoconutalkyl phthalate, heptylnonylphthalate, octyldecanoyl phthalate, octyldecyl phthalate,isooctylisodecyl phthalate, dimethyl phthalate, diethyl phthalate,di-n-butyl phthalate, diisobutyl phthalate, di-2-ethylhexyl phthalate,dihexyl phthalate, bis(3,5,5-trimethylhexyl) phthalate, dicyclohexylphthalate, diheptyl phthalate, di-n-octyl phthalate, diisooctylphthalate, dinonyl phthalate, diisononyl phthalate, diisodecylphthalate, dicapryl phthalate, dilauryl phthalate, diundecyl phthalate,ditridecyl phthalate, diphenyl phthalate, dimethoxyethyl phthalate,butylbenzyl phthalate, butylphenylmethyl phthalate, C₇/C₉ alkylbenzylphthalate, isodecylbenzyl phthalate, texanolbenzyl phthalate,7-(2,6,6,8-tetramethyl-4-oxa-3-oxo-nonyl)benzyl phthalate,bis(diethyleneglycolmonomethylether) phthalate, dimethylglycolphthalate, triethyl citrate, acetyltriethyl citrate, tributyl citrate,acetyltributyl citrate, tricapryl trimellitate, trioctyl trimellitate,triisononyl trimellitate, tridecyl trimellitate, triisodecyltrimellitate, heptylnonyl trimellitate, methylphthalyl ethyleneglycolate, ethylphthalyl ethylene glycolate, butylphthalyl ethyleneglycolate, glycerol triacetate, benzphenol, and mixtures thereof (e.g.,about 20% by weight of dimethyl succinate, 21% by weight of dimethyladipate and about 59% by weight of dimethyl glutarate);

e) mono-, di-, or polyesters of fatty acids having about 8 or morecarbon atoms with di-, tri-, or polyhydric alcohols, such as glycerinmonostearate, glycerin 12-hydroxy stearate, glycerin distearate,diglycerin monostearate, tetraglycerin monostearate, glycerinmonolaurate, diglycerin monolaurate, and tetraglycerin monolaurate;

f) diesters of α,ω-diols where the acid can be linear or branched chainalkanoic acid having about 1-6 carbon atoms or aromatic acid and thediol can be linear of branched chain aliphatic diol, such as diethyleneglycol dibenzoate, dipropylene glycol dibenzoate, polyethylene glycoldibenzoate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIBavailable from Eastman Chemical Company of Kingsport, Tenn.) anddiethylene glycol dibenzoate, 2,2,4-trimethyl-1,3-pentanediolmonoisobutyrate benzoate,

g) mono- and di-alkyl (such as C₁-C₆) glycol ethers of alkylene andpolyalkylene glycols, and analogs of such glycol ethers as some of thepolyol telechelics disclosed herein, such as monomethyl diethyleneglycol, monoethyl dipropylene glycol, and monomethyltripropylene glycol;

h) alkoxylated alcohols, such as nonyl phenols alkoxylated with about1-50 (such as about 7-12) moles of an alkoxylating agent or mixture ofalkoxylating agents having about 1-6 (such as about 2-4) carbon atoms,alkoxylated bisphenol A like ethoxylated bisphenol A, and propoxylatedtrimethylolpropane, some of which are available from Stepan Company ofNorthfield, Ill.;

i) fatty telechelics such as fatty polyamine telechelics and fattypolyol telechelics disclosed herein, some of which can be liquid atambient temperature, like castor oil, soy and linseed oils;

j) compounds and mixtures having ethylenic unsaturation, such aspolyesters of unsaturated carboxylic acids (e.g., tripropylene glycoldiacrylate, Bisphenol A diglycidylether diacrylate, 1,6-Hexanedioldiacrylate, 1,4-butanediol dimethacrylate, ethyleneglycoldimethacrylate, polyethylene glycol dimethacrylate, diethylene glycoldimethacrylate, urethane dimethacrylate, tetraethylene glycoldimethacrylate, triethylene glycol dimethacrylate, trimethylolpropanetrimethacrylate, pentaerythritol triacrylate, and trimethylolpropanetriacrylate), bismaleimides (e.g., N,N′-m-phenylenedimaleimide),polyamides of unsaturated carboxylic acids, esteramides of unsaturatedcarboxylic acids, allyl esters of cyanurates (e.g., triallyl cyanurate),allyl esters of isocyanurates (e.g., triallyl isocyanurate), allylesters of aromatic acids (e.g., triallyl trimaletate and triallyltrimellitate), liquid vinyl polydienes (e.g, liquid vinyl polybutadienehomopolymers and copolymers having molecular weight of about 1,000 toabout 5,000, such as about 1,800 to about 4,000, or about 2,000 to about3,500, like 90% high vinyl polybutadiene having a molecular weight ofabout 3,200, 70% high vinyl 1,2-polybutadiene having a molecular weightof about 2,400, and 70% high vinyl poly(butadiene-styrene) copolymerhaving a molecular weight of about 2,400), mono- and polyunsaturatedpolycarboxylic acids and anhydrides, monoesters, polyesters, monoamides,polyamides, esteramides, and polyesteramides thereof (e.g., citraconicacid, itaconic acid, fumaric acid, maleic acid, mesaconic acid, aconiticacid, maleic anhydride, itaconic anhydride, citraconic anhydride,poly(meth)acrylic acid, polyitaconic acid, copolymers of (meth)acrylicacid and maleic acid, copolymers of (meth)acrylic acid and styrene, andfatty acids having a C₆ or longer chain, such as hexadecenedioic acid,octadecenedioic acid, vinyl-tetradecenedioic acid, eicosedienedioicacid, dimethyl-eicosedienedioic acid, 8-vinyl-10-octadecenedioic acid,anhydrides thereof, methyl, ethyl, and other linear or branched alkylesters thereof, amides thereof, esteramides thereof, and mixturesthereof), unsaturated oils, polyester diol reaction product ofo-phthalic acid and diethylene glycol, and mixtures thereof;

k) other miscellaneous compounds including alkoxy alkyl esters such asmethoxy propylacetate and ethoxy propylacetate, pyrrolidones such asN-methyl-2-pyrrolidone and N-vinyl-pyrrolidone, monohydroxylatedpolybutadienes, silicones such as dimethicone copolyol esters,dimethiconol esters, and silicone carboxylates, aromatic petroleumcondensate, partially hydrogenated terphenyls, guerbet esters, cyclicesters, cyclic ethers, and/or cyclic amides such as those disclosedherein; and

l) mixtures of two or more compounds chosen from a)-k).

Fillers

As used herein, the term “filler” refers to any compound or compositionor mixture thereof that can be used to vary certain properties ofselected portions of the golf ball, including density or specificgravity, flexural modulus, tensile modulus, tear strength, moment ofinertia, hardness, abrasion resistance, weatherability, volume, weight,etc. The fillers can be in the forms of nano-scale or micro-scalepowders, fibers, filaments, flakes, platelets, whiskers, wires, tubes,or particulates for homogenous dispersion. Suitable fillers for golfballs may be solid or hollow, and include, for example, metal (or metalalloy) powder, metal oxide and salts, ceramics, particulates,carbonaceous materials, polymeric materials, glass microspheres, and thelike or blends thereof. Non-limiting examples of metal (or metal alloy)powders include bismuth, brass, bronze, cobalt, copper, inconel, iron,molybdenum, nickel, stainless steel, titanium, aluminum, tungsten,beryllium, zinc, magnesium, manganese, and tin. Non-limiting examples ofmetal oxides and salts include zinc oxide, iron oxide, aluminum oxide,titanium dioxide, magnesium oxide, zirconium oxide, tungsten trioxide,zirconium oxide, tungsten carbide, tungsten oxide, tin oxide, zincsulfide, zinc sulfate, zinc carbonate, barium sulfate, barium carbonate,calcium carbonate, calcium metasilicate, magnesium carbonate, andsilicates. Non-limiting examples of carbonaceous materials includegraphite and carbon black. Examples of other useful fillers includeprecipitated hydrated silica, boron, clay, talc, glass fibers, aramidfibers, mica, diatomaceous earth, regrind (typically recycled corematerial mixed and ground to 30 mesh particle size), high Mooneyviscosity rubber regrind, and mixtures thereof. Examples of polymericmaterials include, but are not limited to, hollow spheres ormicrospheres of chemically or physically foamed thermoplastic orthermosetting polymers, such as epoxies, urethanes, polyesters,nucleated reaction injection molded polyurethanes or polyureas.

The selection of fillers is in part dependent upon the type of golf balldesired, i.e., one-piece, two-piece, multi-component, or wound. Fillersmay be used to modify the weight of any portion of the golf ball. Thefiller can be inorganic, having a density of greater than 4 g/cc, andcan be present in amounts of 5-65 wt. % of the polymer componentsincluded in the golf ball portion.

Blowing and/or Foaming Agents

The compositions may be foamed by the addition of at least one physicalor chemical blowing or foaming agent. Foamed polymer allows one toadjust the density or mass distribution of the ball to adjust theangular moment of inertia, and, thus, the spin rate and performance ofthe ball. Blowing or foaming agents useful include, but are not limitedto, organic blowing agents such as azobisformamide,azobisisobutyronitrile, diazoaminobenzene,N,N-dimethyl-N,N-dinitrosoterephthalamide,N,N-dinitrosopentamethylenetetramine, benzenesulfonylhydrazide,benzene-1,3-disulfonylhydrazide, diphenylsulfon-3-3,disulfonylhydrazide, 4,4′-oxybisbenzene sulfonylhydrazide, p-toluenesulfonylsemicarbizide, barium azodicarboxylate, butylaminenitrile,nitroureas, trihydrazinotriazine, phenyl-methyl-uranthan,p-sulfonylhydrazide, peroxides, and inorganic blowing agents such asammonium bicarbonate and sodium bicarbonate. A gas, such as air,nitrogen, carbon dioxide, etc., can also be injected into thecomposition during the injection molding process as a blowing agent.

Additionally, foamed compositions may be formed by blending microspheresto the compositions either during or before molding. Polymeric, ceramic,metal, and glass microspheres are useful, and may be solid, hollow,filled, or unfilled. Microspheres up to about 1,000 microns in diametercan be useful. Furthermore, the use of liquid nitrogen for foaming, asdisclosed in U.S. Pat. No. 6,386,992, which is incorporated by referenceherein, may produce highly uniform foamed compositions for use in thepresent disclosure.

Light Stabilizers

The compositions may comprise one or more light stabilizers to preventsignificant yellowing from any unsaturated components contained therein,and to prevent cover surface fractures due to photo-degradation. As usedherein, “light stabilizer” may be understood to include hindered aminelight stabilizers, ultraviolet (UV) absorbers, and antioxidants. Thelight stabilizing component can be used in compositions having adifference in yellowness (ΔY) of about 12 or greater following one-hourexposure to QUV test per ASTM G 154-00a at an irradiance power of 1.00W/m nm, such as about 15 or greater. Light stabilizers can be used invisible layers, such as the outer cover layer, or any internal layerwhen the outer layer(s) are translucent or transparent.

Suitable UV absorbers include Uvinul® DS49 (disodium2,2′-dihydroxy-4,4′-dimethyoxy-5,5′-disulfobenzophenone) and Uvinul®DS50 (2,2′,4,4′-tetrahydroxy-benzophenone) by BASF Corporation; Tinuvin®328 (2-(2′-hydroxy-3′,5′-di(t-amylphenyl)benzotriazole), Tinuvin® 571(2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol), Tinuvin® P(2-(2-hydroxy-5-methylphenyl)benzotriazole), and CGL 1545 (experimentaltriazine derivative) by Ciba Specialty Chemicals Corporation; Sanduvor®PR-25 (dimethyl-4-methoxy-benzylidenemalonate) by Clariant Corporation;Cyasorb® UV-2337 (2-(2′-hydroxy-3′,5′-di(t-amylphenyl)benzotriazole),Cyasorb® UV-1164(2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-octyloxyphenol),and Cyasorb® UV-3638 (2,2′-(1,4-phenylene)-bis(4-3,1-benzoxazin-4-one))by Cytec Industries; Quercetin® (3,3′,4′,5,7-pentahydroxy flavone) by EMIndustries; UV-Chek® AM-300 (2-hydroxy-4-n-octyloxy-benzophenone) andUV-Chek® AM-340(2,4-di(t-butylphenyl)-3,5-di(t-butyl)-4-hydroxybenzoate) by FerroCorporation; Maxgard® DPA-8 (2-ethylhexyl-2-cyano-3,3-diphenylacrylate)by Garrison Industries; Givsorb® 2 (propanedione), Givsorb® 13, Givsorb®14, and Givsorb® 15 by Givaudan-Roure Corporation; Norbloc® 6000(2-(2′-hydroxy-5′-(2-hydroxyethyl)benzotriazole) and Norbloc® 7966(2-(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole) by JessenPharmaceuticals. Suitable light stabilizers include, but are not limitedto, Tinuvin® 622LD (dimethyl succinate polymer with4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol) and Tinuvin® 765(bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate) by Ciba SpecialtyChemicals Corporation; Sanduvor® 3070 (hindered amine) by ClariantCorporation; Cyasorb® UV-3581(3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidylpyrrolidin-2,5-dione) byCytec Industries. For aromatic and unsaturated formulations, the UVabsorber can be Tinuvin® 328, and the hindered amine light stabilizercan be Tinuvin® 765, among others. Light stabilizer for saturatedformulations can be Tinuvin® 292, among others. In addition, Tinuvin®213 and 770, and antioxidants such as Irganox® 1010(tetrakis(3,5-di(t-butyl-hydroxyhydrocinnamate))methane) and Irganox®1135 (C₇₋₉-branched alkyl ester of 3,5-di(t-butyl-4-hydroxyhydrocinnamicacid) by Ciba Specialty Chemicals Corporation and Sandostab® P-EPQ (arylphosphonite) by Clariant Corporation, are also applicable.

Light stabilizers can be used alone or in combinations of two or morethereof, or in combination with coloring agents such as dyes andpigments, as well as optical brighteners, in golf ball compositionsdisclosed herein. Pigments may be fluorescent, autofluorescent,luminescent, or chemoluminescent, and include white pigments such astitanium oxide and zinc oxide. These coloring agents may be added in anyamounts that will achieve their desired purpose.

Freezing Point Depressants

Multi-functional curing agents can be used in the compositions of thepresent disclosure. The multi-functional curing agent can include, or bemodified with, at least one compatible freezing point depressantincluding triols such as trimethylolpropane, tetraols such asN,N,N′,N′-tetrakis(2-hydroxylpropyl)ethylenediamine, primary diaminessuch as 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane and4,4′-diaminodicyclohexylmethane, among others.

Vulcanizing Agents

When the composition of the present disclosure comprise ethylenic and/oracetylenic unsaturation moieties, one or more vulcanizing agents, suchas radical initiators, polyisocyanates, co-crosslinking agent, curativescomprising ethylenic and/or acetylenic unsaturation moieties,cis-to-trans catalysts, organosulfur compounds, and/or processing aids,can be added to the composition, which can then be crosslinked atelevated temperature under increased pressure. Radical initiatorsinclude sulfur-based compounds such as element sulfur and thiazoleaccelerators, carbon-carbon initiators such as those disclosed inco-owned and co-pending application bearing Ser. No. 10/614,325, whichare incorporated herein by reference, and various peroxides including,but are not limited to, diacyl peroxides, ketone peroxides,peroxydicarbonates, peroxyesters, alkyl aralkyl peroxides, diaraylkylperoxides, dialkyl peroxides, hydroperoxides, and peroxyketals.Non-limiting examples of dialkyl peroxides include di-t-amyl peroxide,di-t-butyl peroxide, t-butyl cumyl peroxide, di-cumyl peroxide (DCP),di(2-methyl-1-phenyl-2-propyl) peroxide, t-butyl2-methyl-1-phenyl-2-propyl peroxide,di(t-butylperoxy)-diisopropylbenzene,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,4,4-di(t-butylperoxy)-n-butylvalerate, and mixtures thereof. DCP is themost commonly used peroxide in golf ball manufacturing.Di(t-butylperoxy)-diisopropylbenzene can provide higher crosslinkingefficiency, low odor and longer scorch time, among other properties. DCPcan be blended with di(t-butylperoxy)-diisopropylbenzene. In the pureform, the radical initiator or a blend thereof can be used in an amountof 0.25-10, 0.25-5, or 0.5-2.5 phr by weight of the elastomer.

Polyisocyanates as disclosed herein can be used to crosslink reactivecompositions comprising urethane and/or urea linkages. Isocyanate groupcan react with urethane linkage to form allophanate linkage having ageneral structure of:

or react with urea linkage to form biuret linkage having a generalstructure of:

Polyisocyanate crosslinked compositions can have a material hardness of70 Shore A to 60 Shore D. Sulfur or peroxide cured compositions can havea material hardness of 25-85 Shore A.

Suitable co-crosslinking agents all have di- or polyunsaturation and atleast one readily extractable hydrogen in the α position to theunsaturated bonds. Useful co-crosslinking agents include, but are notlimited to, mono- or polyfunctional unsaturated carboxylate metalliccompounds, polyesters of unsaturated carboxylic acids, polyamides ofunsaturated carboxylic acids, esteramides of unsaturated carboxylicacids, bismaleimides, allyl esters of cyanurates, allyl esters ofisocyanurates, allyl esters of aromatic acids, mono- and polyunsaturatedpolycarboxylic acids, anhydrides of mono- and polyunsaturatedpolycarboxylic acids, monoesters and polyesters of mono- andpolyunsaturated polycarboxylic acids, monoamides and polyamides of mono-and polyunsaturated polycarboxylic acids, esteramides andpolyesteramides of mono- and polyunsaturated polycarboxylic acids,liquid vinyl polydienes, and mixtures thereof. Unsaturated carboxylatemetallic compounds are Type I co-crosslinking agents. They differ fromall others, which are Type II co-crosslinking agent, in their effect onthe curing characteristics of the system. Type I co-crosslinking agentsgenerally form relatively more reactive free radicals which increaseboth cure rate and the state of cure of the system, and form ioniccrosslinks primarily. Type II co-crosslinking agents form relativelyless reactive and more stable free radicals and increase primarily thestate of cure of the elastomer, and primarily form carbon-carboncrosslinks. The co-crosslinking agent can be present in the amount of atleast about 0.1 parts per one-hundred parts by weight of the base rubber(phr), such as about 0.5 phr, 1 phr, 2 phr, 6 phr, 8 phr, 10 phr, 15phr, 20 phr, 25 phr, 30 phr, or 40 phr, and up to about 80 phr, such asup to about 60 phr. The amount of carbon-carbon-crosslinks in theresulting thermoset material can be no less than the amount of ioniccrosslinks.

Unsaturated carboxylate metallic compounds can have one or moreα,β-unsaturated carboxylate functionalities such as acrylates andmethacrylates. The compounds can have one or more metal ions associatedwith one or more of the unsaturated carboxylate functionalities, such asZn, Ca, Co, Fe, Mg, Ti, Ni, Cu, etc. Metallic compounds of difunctionalunsaturated carboxylates include, without limitation, zinc diacrylate(ZDA), zinc dimethacrylate (ZDMA), calcium diacrylate, and a blendthereof. Metallic compounds of polyfunctional unsaturated carboxylatesinclude reaction products of a) mono-basic unsaturated carboxylic acidssuch as acrylic acid and/or methacrylic acid, b) di-basic and/orpolybasic carboxylic acids having mono- or polyunsaturation, and/oranhydrides thereof, such as those disclosed herein below, and c)divalent metal oxide. Examples of such metallic compounds and theirsynthesis are disclosed in U.S. Pat. No. 6,566,483, the entirety ofwhich is incorporated herein by reference.

Unsaturated carboxylic acids can be condensed with polyamines (formingpolyamides), polyols (forming polyesters), or aminoalcohols (formingesteramides). Non-limiting examples of unsaturated carboxylic acidcondensates include tripropylene glycol diacrylate, Bisphenol Adiglycidylether diacrylate, 1,6-Hexanediol diacrylate, 1,4-butanedioldimethacrylate, ethyleneglycol dimethacrylate, polyethylene glycoldimethacrylate, diethylene glycol dimethacrylate, urethanedimethacrylate, tetraethylene glycol dimethacrylate, triethylene glycoldimethacrylate, trimethylolpropane trimethacrylate, pentaerythritoltriacrylate, and trimethylolpropane triacrylate.

Non-limiting example of bismaleimide include N,N′-m-phenylenedimaleimide(HVA-2, available from Dupont). Non-limiting examples of allyl estersinclude triallyl cyanurate (Akrosorb® 19203, available from AkrochemCorp. of Akron, Ohio), triallyl isocyanurate (Akrosorb® 19251, alsoavailable from Akrochem Corp.), and triallyl trimaletate (TATM,available from Sartomer Company of Exton, Pa.). Non-limiting examples ofmono- or polyunsaturated polycarboxylic acids and derivatives thereofinclude citraconic acid, itaconic acid, fumaric acid, maleic acid,mesaconic acid, aconitic acid, maleic anhydride, itaconic anhydride,citraconic anhydride, poly(meth)acrylic acid, polyitaconic acid,copolymers of (meth)acrylic acid and maleic acid, copolymers of(meth)acrylic acid and styrene, and fatty acids having a C₆ or longerchain, such as hexadecenedioic acid, octadecenedioic acid,vinyl-tetradecenedioic acid, eicosedienedioic acid,dimethyl-eicosedienedioic acid, 8-vinyl-10-octadecenedioic acid,anhydrides thereof, methyl, ethyl, and other linear or branched alkylesters thereof, amides thereof, esteramides thereof, and mixturesthereof.

Liquid vinyl polydienes are liquid at ambient temperature, such asliquid vinyl polybutadiene homopolymers and copolymers, and can have lowto moderate viscosity, low volatility and emission, high boiling point(such as greater than 300° C.), and molecular weight of about 1,000 toabout 5,000, such as about 1,800 to about 4,000, or about 2,000 to about3,500. Non-limiting examples of liquid vinyl polydienes include 90% highvinyl polybutadiene having a molecular weight of about 3,200, 0 (70%high vinyl 1,2-polybutadiene having a molecular weight of about 2,400,and 70% high vinyl poly(butadiene-styrene) copolymer having a molecularweight of about 2,400.

The cis-to-trans catalyst or organosulfur compound, such as halogenatedcompound, can be one having cis-to-trans catalytic activity or a sulfuratom (or both), and can be present in the polymeric composition by atleast about 2.2 phr, such as less than about 2.2-5 phr. Useful compoundsof this category include those disclosed in U.S. Pat. Nos. 6,525,141,6,465,578, 6,184,301, 6,139,447, 5,697,856, 5,816,944, and 5,252,652,the disclosures of which are incorporated by reference in theirentirety.

The halogenated organosulfur compound may include pentafluorothiophenol;2-fluorothiophenol; 3-fluorothiophenol; 4-fluorothiophenol;2,3-fluorothiophenol; 2,4-fluorothiophenol; 3,4-fluorothiophenol;3,5-fluorothiophenol 2,3,4-fluorothiophenol; 3,4,5-fluorothiophenol;2,3,4,5-tetrafluorothiophenol; 2,3,5,6-tetrafluorothiophenol;4-chlorotetrafluorothiophenol; pentachlorothiophenol;2-chlorothiophenol; 3-chlorothiophenol; 4-chlorothiophenol;2,3-chlorothiophenol; 2,4-chlorothiophenol; 3,4-chlorothiophenol;3,5-chlorothiophenol; 2,3,4-chlorothiophenol; 3,4,5-chlorothiophenol;2,3,4,5-tetrachlorothiophenol; 2,3,5,6-tetrachlorothiophenol;pentabromothiophenol; 2-bromothiophenol; 3-bromothiophenol;4-bromothiophenol; 2,3-bromothiophenol; 2,4-bromothiophenol;3,4-bromothiophenol; 3,5-bromothiophenol; 2,3,4-bromothiophenol;3,4,5-bromothiophenol; 2,3,4,5-tetrabromothiophenol;2,3,5,6-tetrabromothiophenol; pentaiodothiophenol; 2-iodothiophenol;3-iodothiophenol; 4-iodothiophenol; 2,3-iodothiophenol;2,4-iodothiophenol; 3,4-iodothiophenol; 3,5-iodothiophenol;2,3,4-iodothiophenol; 3,4,5-iodothiophenol; 2,3,4,5-tetraiodothiophenol;2,3,5,6-tetraiodothiophenoland; the metal salts thereof, and mixturesthereof. The metal salt may be zinc, calcium, potassium, magnesium,sodium, and lithium. Pentachlorothiophenol is commercially availablefrom Strucktol Company of Stow, Ohio, and zinc pentachlorothiophenol iscommercially available from eChinachem of San Francisco, Calif.

Processing acids for the crosslinkable compositions include, withoutlimitation, organic acids, metal salts thereof, esters thereof (such aslinear or branched C₁ to C₈ alkyl esters), and alcohols derived fromsuch organic acids, which can be non-volatile and non-migratory. Any ofthe fatty acids, fatty alcohols, fatty esters, and metal cationsdisclosed herein can be used. For example, the processing aid can be oneor more aliphatic, mono-functional, saturated, mono-unsaturated, orpoly-unsaturated organic acids having about 36 carbon atoms or fewer,such as 6-26, 6-18, or 6-12 carbon atoms, and/or metal salts thereof.Metal cations can be one or more alkali metal, transition metal, oralkaline earth metal cations, or a combination of such cations.Non-limiting examples of the organic acids include caproic acid,caprylic acid, capric acid, lauric acid, stearic acid, behenic acid,erucic acid, oleic acid, and linoleic acid. Non-limiting examples of themetal cations include lithium, sodium, potassium, magnesium, calcium,barium, and zinc. Agents other than organic acids/salts may be used, aslong as they also exhibit ionic array plasticizing and ethylenecrystallinity suppression properties. The processing aids can be addedin an amount sufficient to enhance the resilience of the crosslinkableelastomer, and/or substantially eliminate crystallinity therein. Theamount can be at least about 0.1% by weight of the total amount of theelastomer and processing aid, such as 1%, 5%, 15%, 20%, 35%, 40%, and upto 50%. Alternatively, the amount of the processing aids can be 0.25-150phr by weight of the elastomer or blend of elastomers. Other processingaids for crosslinkable compositions include those disclosed in U.S. Pat.No. 5,141,978, which are incorporated herein by reference.

Moisture Scavengers

Moisture scavengers can be low-viscosity, reactive, non-reactive,include isocyanate-containing compounds such as monomeric compounds likep-toluene sulfonyl isocyanate (PTSI from VanDeMark Inc. of Lockport,N.Y.) and polymeric compounds like polymeric methylene diphenyldiisocyanate (PAPI® MDI from Dow Chemical), oxazolidines, oxazolanes,orthoformates such as trimethyl- and triethyl orthoformates,orthoacetates such as trimethyl- and triethyl orthoacetates, alkyl(linear or branched C₁ to C₁₂ alkyls) esters of toluene sulfonic acidsuch as methyl p-toluene sulfonate (MTS), and vinyl silanes. Thesemoisture scavengers can be used alone or in combination thereof, or incombinations with other moisture scavengers such as calcium oxide andmolecular sieves. Amount of the moisture scavengers can be about 10 phror less, such as about 5 phr or less, and can be about 0.01 phr orgreater, such as about 0.05 phr or greater, or about 0.1 phr or greater.Various light stabilizers, UV absorbers, photoinitiators, and silanecrosslinkers are all readily available.

Fragrance Components

As used herein, a material or component is regarded as odorous when itsodor threshold is greater than 0.029 mg/m³ in air. A fragrance ormasking component may be added to compositions comprising such odorousmaterials or components, in an amount of at least 0.01% by weight of thecomposition, such as 0.03%, 0.08%, 0.5%, 1%, 1.2%, 1.5%, or any amountstherebetween. Suitable fragrance components include, but are not limitedto, Long Lasting Fragrance Masks #59672, #46064, and #55248,Non-Descript Fragrance Mask #97779, Fresh and Clean Fragrance Mask#88177, and Garden Fresh Fragrance Mask #87473, available from Flavorand Fragrance Specialties of Mahwah, N.J. Other non-limiting fragrancecomponents include benzaldehyde, benzyl benzoate, benzyl propionate,benzyl salicylate, benzyl alcohol, cinnamic aldehydes, natural andessential oils derived from botanical sources, and mixtures thereof.

Composition Blends

The compositions of the disclosure can be used in amounts of 1-100%,such as 10-90% or 10-75%, to form any portion of the golf ball,optionally in blend with one or more other materials being present inamounts of 1-95%, 10-90%, or 25-90%. The percentages are based on theweight of the portion in question. Conventional materials for golf ballcover, intermediate layer, and core suitable as the other materialsinclude:

-   1) Non-ionomeric acid polymers, such as copolymers E/Y of an olefin    E having 2-8 carbon atoms and a carboxylic acid Y having 3-8 carbon    atoms, or terpolymers E/X/Y having an additional softening    comonomer X. The olefin E can be ethylene, and the acid Y can be    acrylic, methacrylic, crotonic, maleic, fumaric, itaconic acid, or    combinations thereof. The comonomer X can be vinyl esters of    aliphatic carboxylic acids having 2-10 carbon atoms, alkyl ethers,    alkyl acrylates, and alkyl alkylacrylates where alkyl groups can be    linear or branched having 1-10 carbon atoms. Depending on the acid    content by weight, the polymer may be referred to as low acid    (2-10%), medium acid (10-16%), and high acid (16-50%). The    comonomer, when present, may be in an amount of 2-40% by weight of    the acid polymer. Examples include Nucrel® from E. I. Du Pont de    Nemours & Company and Escor® from ExxonMobil.-   2) Anionic and cationic ionomers such as the acid polymers above    partially or fully neutralized with organic or inorganic cations,    such as zinc, sodium, lithium, magnesium, potassium, calcium,    manganese, nickel, ammonium (primary, secondary, tertiary), and the    like. The extent of neutralization can be 1-105% in terms of    stoichiometric ratio of total cation to total anion, such as 50%,    70%, or greater. Examples include Surlyn® from E. I. Du Pont de    Nemours & Company and Iotek® from ExxonMobil, as well as the    material compositions disclosed in U.S. application Ser. No.    09/691,284, now U.S. Pat. No. 6,653,382, U.S. application Ser. No.    10/108,793, now U.S. Publication No. 2003/0050373, U.S. application    Ser. No. 10/230,015, now U.S. Publication No. 2003/0114565, and U.S.    application Ser. No. 10/269,341, now U.S. Publication No.    2003/0130434, the disclosures of which are incorporated herein by    reference in their entirety.-   3) Thermoplastic or thermoset (vulcanized) synthetic or natural    rubbers, including polyolefins and copolymers or blends thereof,    such as balata, polyethylene, polypropylene, polybutylene, isoprene    rubber, ethylene-propylene rubber, ethylene-butylene rubber,    ethylene-propylene-(non-conjugated diene) terpolymers; polystyrenes    and copolymers thereof, such as styrene-butadiene copolymers,    poly(styrene-co-maleic anhydride), acrylonitrile-butylene-styrene    copolymers, poly(styrene sulfonate); and homopolymers or copolymers    produced using single-site catalyst such as metallocene (grafted or    non-grafted).-   4) Polyphenylene oxide resins, polyacrylene ethers, or blends of    polyphenylene oxide with high impact polystyrene such as Noryl® from    General Electric Company.-   5) Aliphatic and/or aromatic thermoplastics, including polyesters,    such as ethylene methylacrylate, ethylene ethylacrylate, ethylene    vinyl acetate, poly(ethylene terephthalate), poly(butylene    terephthalate), poly(propylene terephthalate), poly(trimethylene    terephthalate), modified poly(ethylene terephthalate)/glycol,    poly(ethylene naphthalate), cellulose esters, Hytrel® from E. I. Du    Pont de Nemours & Company, and Lomod® from General Electric Company;    polycarbonates; polyacetals; polyimides; polyetherketones;    polyamideimides; thermoplastic block copolymers (Kraton® rubbers    from Shell Chemical); co-polyetheramides (Pebax® from AtoFina); and    elastomers in general.-   6) Vinyl resins such as polyvinyl alcohols, polyvinyl alcohol    copolymers, polyvinyl chloride, block copolymers of alkenyl    aromatics with vinyl aromatics and polyesteramides, copolymers of    vinyl chloride with vinyl acetate, acrylic esters or vinylidene    chloride.-   7) Polyamides such as poly(hexamethylene adipamide) and others    prepared from diamines, fatty acids, dibasic acids, and amino acids    (like polycaprolactams), and blends of polyamides with Surlyn®,    ethylene homopolymers or copolymers or terpolymers, etc.-   8) Acrylic resins and blends of these resins with polyvinyl chloride    or other elastomers.-   9) Epoxy resins and silicones, including siloxanes and urethane    epoxies such as those disclosed in U.S. Pat. No. 5,908,358, which is    incorporated by reference herein.-   10) Blends and alloys, including blends of polycarbonate and    acrylonitrile-butylene-styrene, blends of polycarbonate and    polyurethane, blends of polyvinyl chloride with    acrylonitrile-butadiene-styrene or ethylene vinyl acetate or other    elastomers, blends of thermoplastic rubbers with polyethylene or    polypropylene.

Preferably, a thermoplastic composition of the present disclosure isblended with one or more thermoplastic materials listed above to formthe golf ball portion. One of ordinary skill in the art would be awareof methods to blend the materials with the compositions of thedisclosure.

Core Compositions

The cores of the golf balls formed according to the disclosure may besolid, semi-solid, hollow, fluid-filled, gas-filled, powder-filled,one-piece or multi-component cores. The term “semi-solid” as used hereinrefers to a paste, a gel, or the like. Any core material known to one ofordinary skill in that art is suitable for use in the golf balls of thedisclosure. Suitable core materials include thermoset materials, such asrubber, styrene butadiene, polybutadiene, isoprene, polyisoprene,trans-isoprene, as well as thermoplastics such as ionomer resins,polyamides, and polyesters, and thermoplastic or thermoset polyurethaneor polyurea elastomers. As mentioned above, the compositions of thepresent disclosure may be incorporated into any portion of the golfball, including the core. For example, an inner core center or a corelayer may comprise at least one of the reactive compositions disclosedherein.

The golf ball core can comprise one or more materials chosen from baserubber (natural, synthetic, or a combination thereof, such aspolybutadiene), crosslinking initiator (such as dialkyl peroxide),co-crosslinking agent (such as those having di- or polyunsaturation andat least one readily extractable hydrogen in the α position to theunsaturated bonds), filler, cis-to-trans catalyst, organosulfurcompound, among others. Choices for these materials are known to oneskilled in the art, such as those disclosed in co-pending andco-assigned U.S. Patent Publication No. 2003/0119989, bearing Ser. No.10/190,705, the disclosure of which is incorporated by reference herein.The core compositions can be used to form any other portions of the golfball, such as one or more of the intermediate layers and cover layers.

Intermediate Layer Compositions

When the golf ball comprises at least one intermediate layer, such asone disposed between the cover and the core, or an inner cover layer orouter core layer, i.e., any layer(s) disposed between the inner core andthe outer cover of the golf ball, this layer can be formed from any oneor more thermoplastic and thermosetting materials known to those ofordinary skill. These materials can be any and all of the compositionsdisclosed herein, including those listed under “Composition Blends”above, as well as those disclosed in U.S. Patent Publication No.2003/0119989 and U.S. Pat. Nos. 5,334,673 and 5,484,870, which are allincorporated by reference herein.

The intermediate layer may include homopolymers or copolymers ofethylene, propylene, butylene, butene, and/or hexene, optionallyincorporating functional monomers such as acrylic and methacrylic acid,optionally being fully or partially neutralized ionomer resins and theirblends, imidized, amino group containing polymers, polycarbonate,reinforced polyamides, polyphenylene oxide, high impact polystyrene,polyether ketone, polysulfone, poly(phenylene sulfide),acrylonitrile-butadiene, acrylic-styrene-acrylonitrile, poly(ethyleneterephthalate), poly(butylene terephthalate), poly(ethylene vinylalcohol), poly(tetrafluoroethylene) and their copolymers includingfunctional comonomers, and blends thereof. The intermediate layer mayinclude at least one ionomer, such as acid-containing ethylene copolymerionomers, including E/X/Y terpolymers where E is ethylene, X is anacrylate or methacrylate-based softening comonomer in 0-50 wt. %, and Yis acrylic or methacrylic acid in 5-35 wt. % (such as 8-35 wt. % or 8-20wt. %).

The acid copolymers can be E/X or E/X/Y copolymers where E is ethylene,X is α,β-ethylenically unsaturated carboxylic acid or a combination oftwo or more thereof, such as having about 3-8 carbon atoms (e.g.,acrylic acid and/or methacrylic acid), and Y is a softening co-monomer,such as alkyl (meth)acrylate where the alkyl group can be linear orbranched and have about 1-8 carbon atoms (e.g., n-butyl). By“softening,” it is meant that the crystallinity is disrupted (thepolymer is made less crystalline). X can be at least about 2 wt. % ofthe copolymer, such as 2-30, 3-30, 4-20, 4-25, 5-20, or 5-20 wt. % ofthe polymer, and Y can be present in 0-30, 3-25, 10-23, 17-40, 20-40, or24-35 wt. % of the acid copolymer.

Soft, resilient ionomers included in this disclosure can be partiallyneutralized ethylene/(meth) acrylic acid/butyl (meth)acrylate copolymershaving a melt index (MI) and level of neutralization that results in amelt-processible polymer that has useful physical properties. Thecopolymers are at least partially neutralized. At least 40%, or at least55%, such as about 70% or about 80% of the acid moiety of the acidcopolymer can be neutralized by one or more alkali metal, transitionmetal, or alkaline earth metal cations, such as lithium, sodium,potassium, magnesium, calcium, barium, or zinc, or a combination of suchcations.

Soft, resilient, thermoplastic, “modified” ionomers are also exemplarymaterials for use in any one or more golf ball portions present in anyconstruction, such as the inner center, inner core layer, intermediatecore layer, outer core layer, intermediate layer, inner cover layer,intermediate cover layer, outer cover layer, and the like andequivalents thereof. The “modified” ionomer can comprise a melt blend of(a) the acid copolymers or the melt processible ionomers made therefromas described above and (b) one or more organic acid(s) or salt(s)thereof, wherein greater than 80%, or greater than 90%, even 100% of allthe acid of (a) and of (b) can be neutralized by one or more cations.Amount of cations in excess of the amount required to neutralize 100% ofthe acid in (a) and (b) can be used to neutralize the acid in (a) and(b). Blends with fatty acids or fatty acid salts can be used.

The organic acids or salts thereof can be added in an amount sufficientto enhance the resilience of the copolymer, and/or substantiallyeliminate crystallinity of the copolymer. The amount can be at leastabout 5% by weight of the total amount of copolymer and organic acid(s),such as at least about 15%, or at least about 20%, and up to about 50%,such as up to about 40% or up to about 35%. Alternatively, the amount ofthe organic acids or salts thereof can be about 25-150 phr by weight ofthe copolymer or blend of copolymers. The non-volatile, non-migratoryorganic acids can be aliphatic, mono-functional, saturated orunsaturated organic acids or salts thereof as described below, such asthose having less than about 36 carbon atoms, like fatty acids (e.g.,stearic acid and oleic acid) or salts thereof. Agents other than organicacids/salts may be used, as long as they also exhibit ionic arrayplasticizing and ethylene crystallinity suppression properties.

Processes for fatty acid/salt modifications are known in the art. Themodified highly-neutralized soft, resilient acid copolymer ionomers canbe produced by:

-   -   (a) melt-blending 1) ethylene, α,β-ethylenically unsaturated C₃        to C₈ carboxylic acid copolymer(s) or melt-processible        ionomer(s) thereof, optionally having crystallinity disrupted by        addition of a softening monomer or other means, with 2)        sufficient amount of non-volatile, non-migratory organic acids        to substantially enhance the resilience and to disrupt or remove        the remaining ethylene crystallinity, and then, concurrently or        subsequently; and    -   (b) adding a sufficient amount of a cation source to increase        the level of neutralization of all the acid moieties (including        those in the acid copolymer and in the organic acid if the        non-volatile, non-migratory organic acid is an organic acid) to        the desired level.

The ethylene-acid copolymers with high levels of acid (X) are difficultto prepare in continuous polymerizers because of monomer-polymer phaseseparation. This difficulty can be avoided however by use of “co-solventtechnology” as described in U.S. Pat. No. 5,028,674, or by employingsomewhat higher pressures than those which copolymers with lower acidcan be prepared. The weight ratio of X to Y in the composition can be atleast about 1:20, such as at least about 1:15, or at least about 1:10,and up to about 2:1, such as up to about 1.2:1, up to about 1:1.67, upto about 1:2, or up to about 1:2.2.

The acid copolymers can be “direct” acid copolymers (containing highlevels of softening monomers). As noted above, the copolymers can bepartially, highly, or fully neutralized, such as at least about 40%,45%, 50%, 55%, 70, 80%, 90%, or 100% neutralized. The MI of the acidcopolymer should be sufficiently high so that the resulting neutralizedresin has a measurable MI in accord with ASTM D-1238, condition E, at190° C., using a 2160 gram weight, such as at least about 0.1 g/10 min,at least about 0.5 g/10 min, or about 1 g/10 min or greater. In highlyneutralized acid copolymer, the MI of the acid copolymer base resin canbe at least about 20 g/10 min, at least 40 g/10 min, at least 75 g/10min, at least 100 g/10 min, or at least 150 g/10 min.

Specific acid-copolymers include ethylene/(meth)acrylic acid/n-butyl(meth)acrylate, ethylene/(meth) acrylic acid/iso-butyl (meth)acrylate,ethylene/(meth) acrylic acid/methyl (meth) acrylate, and ethylene/(meth)acrylic acid/ethyl (meth)acrylate terpolymers. The organic acids andsalts thereof employed can be aliphatic, mono-functional (saturated,mono-unsaturated, or poly-unsaturated) organic acids, including thosehaving fewer than 36 carbon atoms, such as 6-26, 6-18, or 6-12 carbonatoms. The salts may be any of a wide variety, including the barium,lithium, sodium, zinc, bismuth, potassium, strontium, magnesium andcalcium salts of the organic acids. Non-limiting examples of the organicacids include caproic acid, caprylic acid, capric acid, lauric acid,stearic acid, behenic acid, erucic acid, oleic acid, and linoleic acid.Other fatty acids and salts thereof include any and all of thosedisclosed herein above, such as fatty polyacids and polymerized fattypolyacids (e.g., dimer diacids) and salts thereof. Partial esters ofpolyacids (i.e., having at least one un-esterified acid group) and saltsthereof are also useful. When mono- and/or poly-unsaturated organicacids and/or salts thereof are used, the ionomer composition can becrosslinked into a thermoset material using reactants known to oneskilled in the art, such as peroxide and/or sulfur initiators, some ofwhich are disclosed herein. Alternatively, radiations such as electronbeam radiation and others disclosed herein can be used to crosslink theionomer composition. Optional additives include acid copolymer wax(e.g., Allied wax AC 143 believed to be an ethylene/16-18% acrylic acidcopolymer with a number average molecular weight of 2,040), which assistin preventing reaction between the filler materials (e.g., ZnO) and theacid moiety in the ethylene copolymer, TiO₂ (a whitening agent), opticalbrighteners, etc.

Ionomers may be blended with conventional ionomeric copolymers andterpolymers, and non-ionomeric thermoplastic resins. The non-ionomericthermoplastic resins include, without limit, thermoplastic elastomerssuch as polyurethane, poly-ether-ester, poly-amide-ether,polyether-urea, PEBAX (a family of block copolymers based onpolyether-block-amide, commercially supplied by Atochem),styrene-butadiene-styrene (SBS) block copolymers,styrene(ethylene-butylene)-styrene block copolymers, etc., poly amide(oligomeric and polymeric), polyesters, polyolefins including PE, PP,E/P copolymers, etc., ethylene copolymers with various comonomers, suchas vinyl acetate, (meth)acrylates, (meth)acrylic acid,epoxy-functionalized monomer, CO, etc., functionalized polymers withmaleic anhydride grafting, epoxidization etc., elastomers such as EPDM,metallocene catalyzed PE and copolymer, ground up powders of thethermoset elastomers, etc. Such thermoplastic blends can comprise about1% to about 99% by weight of a first thermoplastic and about 99% toabout 1% by weight of a second thermoplastic.

Thermoplastic polymer components, such as copolyetheresters,copolyesteresters, copolyetheramides, elastomeric polyolefins, styrenediene block copolymers and their hydrogenated derivatives,copolyesteramides, thermoplastic polyurethanes, such ascopolyetherurethanes, copolyesterurethanes, copolyureaurethanes,epoxy-based polyurethanes, polycaprolactone-based polyurethanes,polyureas, and polycarbonate-based polyurethanes fillers, and otheringredients, if included, can be blended in either before, during, orafter the acid moieties are neutralized. Examples of these materials aredisclosed in U.S. Pat. Nos. 6,565,466 and 6,565,455, which areincorporated herein by reference. In addition, polyamides, discussed inmore detail below, may also be blended with ionomers.

The intermediate layer composition may include 1-99 phr (such as 5-90phr, 10-75 phr, or 10-50 phr) of at least one grafted metallocenecatalyzed polymer and 99-1 phr (such as 95-10 phr, 90-25 phr, or 90-50phr) of at least one ionomer. The intermediate layer composition mayalso include at least one ionomer and at least one primarily or fullynon-ionomeric thermoplastic material, such as polyamides, polyamideblends, grafted and non-grafted metallocene catalyzed polyolefins andpolyamides, polyamide/ionomer blends, polyamide/non-ionomer blends,polyphenylene ether/ionomer blends, and mixtures thereof, like thosedisclosed in co-pending U.S. Patent Publication No. 2003/0078348, thedisclosure of which is incorporated by reference herein. One example ofa polyamide/non-ionomer blend is a polyamide and non-ionic polymersproduced using non-metallocene single-site catalysts. As used herein,the term “non-metallocene catalyst” or “non-metallocene single-sitecatalyst” refers to a single-site catalyst other than a metallocenecatalyst. Examples of suitable single-site catalyzed polymers aredisclosed in U.S. Pat. No. 6,476,130, of which the disclosure isincorporated by reference herein. The intermediate layer may also beformed from the compositions as disclosed in U.S. Pat. No. 5,688,191,the disclosure of which is incorporated by reference herein.

The intermediate layer may also be formed of a binding material and aninterstitial material distributed in the binding material, wherein theeffective material properties of the intermediate layer can be differentfor applied forces normal to the surface of the ball from applied forcestangential to the surface of the ball. Examples of this type ofintermediate layer are disclosed in U.S Patent Publication No.2003/0125134, the entire disclosure of which is incorporated byreference herein. At least one intermediate layer may also be a moisturebarrier layer, such as the ones described in U.S. Pat. No. 5,820,488,which is incorporated by reference herein.

Cover Compositions

Obviously, one or more of the cover layers may be formed, at least inpart, from the compositions of the present disclosure. The cover layersinclude outer cover layer, inner cover layer, and any intermediate layerdisposed between the inner and outer cover layers. The covercompositions can include one or more of the polyurethane prepolymers,polyurea prepolymers, poly(urethane-co-urea) prepolymers,polyisocyanates, curatives, and additives. Other materials useful incover composition blends include those disclosed herein for the core andthe intermediate layer.

Golf Ball Constructions

The golf ball can have any construction, including, but not limited to,one-piece, two-piece, three-piece, four-piece, and other multi-piecedesigns. The golf ball can have a single core, a 2-layer core, a 3-layercore, a 4-layer core, a 5-layer core, a 6-layer core, a multi-layercore, a single cover, a 2-layer cover, a 3-layer cover, a 4-layer cover,a 5-layer cover, a 6-layer cover, a multi-layer cover, a multi-layercover, and/or one or more intermediate layers. The compositions of thedisclosure may be used in any one or more of these golf ball portions,each of which may have a single-layer or multi-layer structure. As usedherein, the term “multi-layer” means at least two layers.

Any of these portions can be one of a continuous layer, a discontinuouslayer, a wound layer, a molded layer, a lattice network layer, a web ornet, an adhesion or coupling layer, a barrier layer, a layer ofuniformed or non-uniformed thickness, a layer having a plurality ofdiscrete elements such as islands or protrusions, a solid layer, ametallic layer, a liquid-filled layer, a gel-filled portion, apowder-filled portion, a gas-filled layer, a hollow portion, or a foamedlayer.

In addition, when the golf ball of the present disclosure includes anintermediate layer, this layer may be incorporated with a single ormultilayer cover, a single or multi-piece core, with both a single layercover and core, or with both a multilayer cover and a multilayer core.The intermediate layer may be an inner cover layer or outer core layer,or any other layer(s) disposed between the inner core and the outercover of a golf ball. As with the core, the intermediate layer may alsoinclude a plurality of layers. It will be appreciated that any number ortype of intermediate layers may be used, as desired.

The intermediate layer may also be a tensioned elastomeric materialwound around a solid, semi-solid, hollow, fluid-filled, or powder-filledcenter. As used herein, the term “fluid” refers to a liquid or gas andthe term “semi-solid” refers to a paste, gel, or the like. A wound layermay be described as a core layer or an intermediate layer for thepurposes of the disclosure. The would layer may be formed from acomposition of the disclosure having at least one hydrophobic backboneor segment for improved water resistance. The tensioned elastomericmaterial may also be formed of any suitable material known to those ofordinary skill in the art, such as a polybutadiene reaction product,conventional polyisoprene, solvent spun polyether urea as disclosed inU.S. Pat. No. 6,149,535, or a high tensile filament as disclosed inco-pending U.S. Patent Publication No. 2002/0160859, or coated with abinding material to improve adhere to the core and cover, as disclosedin U.S. Patent Publication No. 2002/0160862. The disclosures of theabove-mentioned patents and publications are incorporated by referenceherein.

While hardness gradients can be used in a golf ball to achieve certaincharacteristics, the present disclosure also contemplates thecompositions of the disclosure being used in a golf ball with multiplecover layers having essentially the same hardness, wherein at least oneof the layers can be modified in some way to alter a property thataffects the performance of the ball. Such ball constructions aredisclosed in co-pending U.S. Application Publication No. 2003/0232666and incorporated by reference herein. Other non-limiting golf ballconstructions include those described in U.S. Pat. Nos. 6,548,618,6,149,535, 6,056,842, 5,981,658, 5,981,654, 5,965,669, 5,919,100,5,885,172, 5,803,831, 5,713,801, 5,688,191, as well as in U.S.Application Publication Nos. 2002/0025862 and 2001/0009310, thedisclosures of which are incorporated by reference herein.

Methods of Forming Layers

The golf balls of the disclosure may be formed using a variety ofapplication techniques such as compression molding, flip molding,injection molding, retractable pin injection molding, reaction injectionmolding (RIM), liquid injection molding (LIM), casting, vacuum forming,powder coating, flow coating, spin coating, dipping, spraying, and thelike. Conventionally, compression molding and injection molding areapplied to thermoplastic materials, whereas RIM, liquid injectionmolding, and casting are employed on thermoset materials. These andother manufacture methods are disclosed in U.S. Pat. Nos. 6,207,784 and5,484,870, the disclosures of which are incorporated herein byreference.

The compositions of the disclosure may be formed over the core using acombination of casting and compression molding. For example, U.S. Pat.No. 5,733,428, the disclosure of which is hereby incorporated byreference, discloses a suitable method for forming a polyurethane coveron a golf ball core. Because this method relates to the use of bothcasting thermosetting and thermoplastic material as the golf ball cover,wherein the cover is formed around the core by mixing and introducingthe material in mold halves, other reactive liquid compositions such aspolyurea compositions may also be used employing the same castingprocess. Once the polyurea composition is mixed, an exothermic reactioncommences and continues until the material is solidified around thecore. Viscosity can be measured over time, so that the subsequent stepsof filling each mold half, introducing the core into one half andclosing the mold can be timed in order to center the core and achieveoverall uniformity. A suitable viscosity range for molding the reactivecomposition can be about 2,000-30,000 cP, such as about 8,000-15,000 cP.

For illustration, the prepolymer and curative can be mixed in amotorized mixer inside a mixing head by metering amounts of the curativeand prepolymer through the feed lines. Top preheated mold halves can befilled and placed in fixture units using centering pins moving intoapertures in each mold half. At a later time, the cavity of a bottommold half, or the cavities of a series of bottom mold halves, can befilled with similar mixture amounts as used in the top mold halves.After the reacting materials have resided in top mold halves for about40-100 seconds, such as about 50-90 seconds, about 60-80 seconds, orabout 70-80 seconds, golf ball subassemblies such as cores can belowered at a controlled speed into the reacting mixture. Ball cups canhold the subassemblies by applying reduced pressure (or partial vacuum).Upon location of the subassemblies in the top mold halves after gellingfor about 4-12 seconds, such as about 5-10 seconds, the vacuum can bereleased to release the subassembly. The top mold halves can then beremoved from the centering fixture unit, inverted and mated with thebottom mold halves having a selected quantity of reacting compositiongelling therein. Other non-limiting molding techniques include thosedisclosed in U.S. Pat. Nos. 5,006,297 and 5,334,673, and others known tothose skilled in the art, which are incorporated herein by reference.

Injection molding and/or compression molding may be used. For example,half-shells of thermoplastic compositions may be made by injectionmolding or compression molding in conventional half-shell molds, thenplaced about the pre-formed subassembly within a compression moldingmachine, and compression molded at about 250-400° F. The molded ballscan then be cooled in the mold and removed when the molded layer is hardenough to be handled without deforming. Prior to forming the layer, thesubassembly may be surface treated to increase the adhesion between thesubassembly and the molded layer. Examples of surface treatmenttechniques can be found in U.S. Pat. No. 6,315,915, which areincorporated by reference.

Dimples

The use of various dimple patterns and profiles provides a relativelyeffective way to modify the aerodynamic characteristics of a golf ball.As such, the manner in which the dimples are arranged on the surface ofthe ball can be by any available method. Non-limiting dimple patternsinclude icosahedral (U.S. Pat. No. 4,560,168), octahedral (U.S. Pat. No.4,960,281), phyllotactic (U.S. Pat. No. 6,338,684), and Archimedean(U.S. Pat. No. 6,705,959) with non-linear parting line, includingtruncated octahedron, great rhombcuboctahedron, truncated dodecahedron,and great rhombicosidodecahedron. The dimples can be circular and/ornon-circular, such as amorphous (U.S. Pat. No. 6,409,615), have tubularlattice pattern (U.S. Pat. No. 6,290,615), having catenary curvature(U.S. Patent Publication No. 2003/0114255), have varying sizes (U.S.Pat. Nos. 6,358,161 and 6,213,898), and/or have high percentage ofsurface coverage (U.S. Pat. Nos. 5,562,552, 5,575,477, 5,957,787,5,249,804, and 4,925,193). These disclosures are all incorporated byreference herein.

Golf Ball Post-Processing

The golf balls of the present disclosure may be painted, coated, orsurface treated for further advantages. The use of light stable reactivecompositions may obviate the need for certain post-processing such asapplying pigmented coating or clear topcoat, thus reducing cost andproduction time, reducing use of volatile organic compounds (VOCs), andimproving labor efficiency. Toning the golf ball cover with titaniumdioxide can enhance its whiteness. The cover can be subjected to suchsurface treatment as corona treatment, plasma treatment, UV treatment,flame treatment, electron beam treatment, and/or applying one or morelayers of clear paint, which optionally may contain one or morefluorescent whitening agents. Trademarks and/or other indicia may bestamped, i.e., pad-printed, on the cover, and then covered with one ormore clear coats for protection and glossy look. UV treatment can beused to cure UV-curable topcoat and/or ink layer (used as a paint layeror a discrete marking tool for logo and indicia), as disclosed in, forexample, U.S. Pat. Nos. 6,500,495, 6,248,804, and 6,099,415. One or moreportions of the golf ball may be subjected to dye sublimation, asdisclosed in U.S. Patent Publication No. 2003/0106442, and/or lasermarking or ablation, as disclosed in U.S. Pat. Nos. 5,248,878 and6,462,303. The disclosures of these patents and publications areincorporated by reference herein.

Golf Ball Properties

Physical properties of each golf ball portion, such as hardness,modulus, compression, and thickness/diameter, can affect playcharacteristics such as spin, initial velocity, and feel. It should beunderstood that the ranges herein are meant to be intermixed with oneanother, i.e., the low end of one range may be combined with the highend of another range.

Component Dimensions

Golf balls and portions thereof of the present disclosure can have anydimensions, i.e., thickness and/or diameter. While USGA specificationslimit the size of a competition golf ball to 1.68 inches or greater indiameter, golf balls of any sizes smaller or larger can be used forleisure play. As such, the golf ball diameter can be 1.68-1.8 inches,1.68-1.76 inches, 1.68-1.74 inches, or 1.7-1.95 inches. Golf ballsubassemblies comprising the core and one or more intermediate layerscan have a diameter of 80-98% of that of the finished ball. The core mayhave a diameter of 0.09-1.65 inches, such as 1.2-1.63 inches, 1.3-1.6inches, 1.4-1.6 inches, 1.5-1.6 inches, or 1.55-1.65 inches.Alternatively, the core diameter can be 1.54 inches or greater, such as1.55 inches or greater, or 1.59 inches or greater, and 1.64 inches orless. The core diameter can be 90-98% of the ball diameter, such as94-96%. When the core comprises an inner center and at least one outercore layer, the inner center can have a diameter of 0.9 inches orgreater, such as 0.09-1.2 inches or 0.095-1.1 inches, and the outer corelayer can have a thickness of 0.13 inches or greater, such as 0.1-0.8inches, or 0.2 or less, such as 0.12-0.01 inches or 0.1-0.03 inches.Two, three, four, or more of outer core layers of different thicknesssuch as the ranges above may be used in combination.

Thickness of the intermediate layer may vary widely, because it can beany one of a number of different layers, e.g., outer core layer, innercover layer, wound layer, and/or moisture/vapor barrier layer. Thethickness of the intermediate layer can be 0.3 inches or less, such as0.1 inches, 0.09 inches, 0.06 inches, 0.05 inches, or less, and can be0.002 inches or greater, such as 0.01 inches or greater. Theintermediate layer thickness can be 0.01-0.045 inches, 0.02-0.04 inches,0.025-0.035 inches, 0.03-0.035 inches. Two, three, four, or more ofintermediate layers of different thickness such as the ranges above maybe used in combination. The core and intermediate layer(s) together forman inner ball, which can have a diameter of 1.48 inches or greater, suchas 1.5 inches, 1.52 inches, or greater, or 1.7 inches or less, such as1.66 inches or less.

The cover thickness can be 0.35 inches or less, such as 0.12 inches, 0.1inches, 0.07 inches, or 0.05 inches or less, and 0.01 inches or greater,such as 0.02 inches or greater. The cover thickness can be 0.02-0.05inches, 0.02-0.045 inches, or 0.025-0.04 inches, such as about 0.03inches. Thickness ratio of the intermediate layer (e.g., as an innercover layer) to the cover (e.g., as an outer cover layer) can be 10 orless, such as 3 or less, or 1 or less.

Hardness

Golf balls can comprise layers of different hardness, e.g., hardnessgradients, to achieve desired performance characteristics. The hardnessof any two adjacent or adjoined layers can be the same or different. Oneof ordinary skill in the art understands that there is a differencebetween “material hardness” and “hardness, as measured directly on agolf ball.” Material hardness is defined by the procedure set forth inASTM-D2240 and generally involves measuring the hardness of a flat“slab” or “button” formed of the material in question. Hardness, whenmeasured directly on a golf ball (or other spherical surface) isinfluenced by a number of factors including, but not limited to, ballconstruction (i.e., core type, number of core and/or cover layers,etc.), ball (or sphere) diameter, and the material composition ofadjacent layers, and can therefore be different from the materialhardness. The two hardness measurements are not linearly related and,therefore, cannot easily be correlated.

The cores of the present disclosure may have varying hardness dependingat least in part on the golf ball construction. The core hardness asmeasured on a formed sphere can be at least 15 Shore A, such as at least30 Shore A, about 50 Shore A to about 90 Shore D, about 80 Shore D orless, about 30-65 Shore D, or about 35-60 Shore D. The intermediatelayer(s) of the present disclosure may also vary in hardness, dependingat least in part on the ball construction. The hardness of theintermediate layer can be about 30 Shore D or greater, such as about 50Shore D or greater, about 55 Shore D or greater, or about 65 Shore D orgreater, and can be about 90 Shore D or less, such as about 80 Shore Dor less or about 70 Shore D or less, or about 55-65 Shore D. Theintermediate layer can be harder than the core layer, having a ratio ofhardness of about 2 or less, such as about 1.8 or less, or about 1.3 orless. The intermediate layer can be different (i.e., harder or softer)than the core layer with a hardness difference of at least 1 unit inShore A, C, or D, such as at least 3 units, or at least 5 units, or atleast 8 units, or at least 10 units, or less than 20 units, or less than10 units, or less than 5 units.

The hardness of the cover layer may vary, depending at least in part onthe construction and desired characteristics of the golf ball. On theShore C scale, the cover layer may have a hardness of about 70 Shore Cor greater, such as about 80 Shore C or greater, and about 95 Shore C orless, such as about 90 Shore C or less.

The difference or ratio of hardness between the cover layer and theinner ball can be manipulated to influence the aerodynamics and/or spincharacteristics of a ball. When the intermediate layer (such as innercover layer) is at least harder than the cover layer (such as outercover layer), or intended to be the hardest portion in the ball, e.g.,about 50-75 Shore D, the cover layer may have a material hardness ofabout 20 Shore D or greater, such as about 25 Shore D or greater, orabout 30 Shore D or greater, or the cover hardness as measured on theball can be about 30 Shore D or greater, such as about 30-70 Shore D,about 40-65 Shore D, about 40-55 Shore D, less than about 45 Shore D,less than about 40 Shore D, about 25-40 Shore D, or about 30-40 Shore D.The material hardness ratio of softer layer to harder layer can be about0.8 or less, such as about 0.75, about 0.7, about 0.5, about 0.45, orless. When the intermediate layer and the cover layer have substantiallythe same hardness, the material hardness ratio can be about 0.9 orgreater, and up to 1.0, and the cover layer may have a hardness of about55-65 Shore D. Alternatively, the cover layer can be harder than theintermediate layer, with the hardness ratio of the cover layer to theintermediate layer being about 1.33 or less, such as about 1.14 or less.

The core may be softer than the cover. For example, the cover hardnessmay be about 50-80 Shore D, and the core hardness may be about 30-50Shore D, with the hardness ratio being about 1.75 or less, such as about1.55 or less or about 1.25 or less.

Compression

As used herein, the terms “Atti compression” or “compression” refers tothe deflection of an object or material relative to the deflection of acalibrated spring, as measured with an Atti Compression Gauge availablefrom Atti Engineering Corp. of Union City, N.J. Compression values ofthe golf ball or portion thereof can be at least in part dependent onthe diameter. Atti compression of the core or portion thereof can be 80or less, such as 75 or less, 40-80, 50-70, 50 or less, 25 or less, 20 orless, 10 or less, or 0, or below the measurable limit of the AttiCompression Gauge. The core or portion thereof may have a Soft CenterDeflection Index (SCDI) compression of 160 or less, such as 40-160 or60-120. The golf ball can have an Atti compression of 40 or greater,such as 55 or greater, 50-120, 60-120, 50-120, 60-100, 75-95, or 80-95.

Initial Velocity and COR

USGA limits the initial velocity of a golf ball up to 250±5 ft/s. Theinitial velocity of the golf ball of the present disclosure can be245-255 ft/s, or greater, such as 250 ft/s or greater, 253-254 ft/s, orabout 255 ft/s. Coefficient of restitution (COR) of a ball or a portionthereof is measured by taking the ratio of the outbound or reboundvelocity to the inbound or incoming velocity (such as, but not limitedto, 125 ft/s). COR can be maximized so that the initial velocity iscontained with a certain limit. COR of the golf ball can be 0.7 orgreater at an inbound velocity of 125 ft/s, such as 0.75 or greater,0.78 or greater, 0.8 or greater, and up to about 0.85, such as0.8-0.815. The core and/or the inner ball can have a COR of 0.78 ormore, such as 0.79 or greater.

Spin Rate

Spin rate of a golf ball can at least in part be dependent onconstruction, and can vary off different golf clubs (e.g., driver,woods, irons, wedges, etc.). In a multi-layer (e.g., 2-piece, 3-piece,4-piece, wound) ball, the driver spin rate can be 2,700 rpm or greater,such as 2,700-3,300 rpm, 2,800-3,500 rpm, 2,900-3,400 rpm, or less than2,700 rpm. Non-limiting measurements of spin rate are disclosed in U.S.Pat. Nos. 6,500,073, 6,488,591, 6,286,364, and 6,241,622, which areincorporated by reference herein.

Flexural Modulus

As used herein, the term “flexural modulus” or “modulus” refers to theratio of stress to strain within the elastic limit (measured in flexuralmode) of a material, indicates the bending stiffness of the material,and is similar to tensile modulus. Flexural modulus, typically reportedin Pascal (“Pa”) or pounds per square inch (“psi”), is measured inaccordance to ASTM D6272-02.

The intermediate layer (e.g., outer core layer, inner cover layer) canhave any flexural modulus of 500-500,000 psi, such as 1,000-250,000 psior 2,000-200,000 psi. The flexural modulus of the cover layer (e.g.,outer cover layer, inner cover layer, intermediate cover layer) can be2,000 psi or greater, such as 5,000 psi or greater, 10,000-150,000 psi,15,000-120,000 psi, 18,000-110,000 psi, 100,000 psi or less, 80,000 orless, 70,000 psi or less, 10,000-70,000 psi, 12,000-60,000 psi, or14,000-50,000 psi.

The cover layer (e.g., inner cover, intermediate cover, outer coverlayers) can have any flexural modulus, such as the numerical rangesillustrated for intermediate layer above. When the cover layer has ahardness of 50-60 Shore D, the flexural modulus can be 55,000-65,000psi. In multi-layer covers, the cover layers can have substantially thesame hardness but different flexural moduli. The difference in flexuralmodulus between any two cover layers can be 10,000 psi or less, 5,000psi or less, or 500 psi or greater, such as 1,000-2,500 psi. The ratioin flexural modulus of the intermediate layer to the cover layer can be0.003-50, such as 0.006-4.5 or 0.11-4.5.

Specific Gravity

The specific gravity of a cover or intermediate layer can be at least0.7, such as 0.8 or greater, 0.9 or greater, 1 or greater, 1.05 orgreater, or 1.1 or greater. The core may have a specific gravity of 1 orgreater, such as 1.05 or greater. In one example, the intermediate layerhas a specific gravity of 0.9 or greater and the cover has a specificgravity of 0.95 or greater. In another example, the core specificgravity is 1.1 or greater and the cover specific gravity is about 0.95or greater.

Adhesion Strength

The adhesion, or peel, strength of the compositions as presentlydisclosed can be 5 lbf/in or greater, such as 10 lbf/in or greater, 20lbf/in or greater, 24 lbf/in or greater, or 26 lbf/in or greater, orlbf/in or less, such as 25 lbf/in, 20 lbf/in, or less. Adhesion strengthof a golf ball layer can be assessed using cross-hatch test (i.e.,cutting the material into small pieces in mutually perpendiculardirections, applying a piece of adhesive cellophane tape over thematerial, rapidly pulling off the tape, and counting the number ofpieces removed) and repeated ball impact test (i.e., subjecting thefinished golf ball to repeated impact and visually examining the coatingfilm for peeling), as disclosed in U.S. Pat. No. 5,316,730, which isincorporated by reference herein.

Water Resistance

Water resistance of a golf ball portion can be reflected by absorption(i.e., weight gain following a period of exposure at a specifictemperature and humidity differential) and transmission (i.e., watervapor transmission rate (WVTR) according to ASTM E96-00, which refers tothe mass of water vapor that diffuses into a material of a giventhickness per unit area per unit time at a specific temperature andhumidity differential). The golf ball or a portion thereof can have aweight gain of 0.15 g or less, such as 0.13 g, 0.09 g, 0.06 g, 0.03 g,or less, and a diameter gain of 0.001 inches or less, over seven weeksat 100% relative humidity and 72° F. The golf ball portion such as theouter or inner cover layer can have a WVTR of 2 g/(m²×day) or less, suchas 0.45-0.95 g/(m²×day), 0.01-0.9 g/(m²×day), or less, at 38° C. and 90%relative humidity.

Shear/Cut Resistance

The shear/cut resistance of a golf ball portion (e.g., inner or outercover layer) may be determined using a shear test having a scale from 1to 6 in damage and appearance. The cover layer can have a number of 3,2, 1, or less on the shear test scale.

Light Stability

Light stability (such as to UV irradiance power of 1.00 W/m²/nm) of thecover layer (e.g., a visible layer such as an outer cover layer or aninner/intermediate cover layer having transparent or translucent outercover layers) may be quantified using difference in yellowness index(ΔYI, according to ASTM D1925) before and after a predetermined period(such as 120 hrs) of exposure. The ΔYI of the cover layer can be 10 orless, such as 6, 4, 2, 1, or less. Difference in yellow-to-blue chromadimension before and after the exposure (Δb*) can also quantify lightstability. The Δb* of the cover layer can be 4 or less, such as 3, 2, 1,or less.

EXAMPLES

The following non-limiting examples are included herein merely forillustration, and are not to be construed as limiting the scope of thepresent disclosure.

Example 1 Saturated Polyurethane Golf Ball Cover

Golf balls comprising a saturated polyurethane cover were made followingthe teachings of U.S. Pat. No. 5,733,428. Cover composition andproperties of cover and ball are listed below.

TABLE 1 GOLF BALLS WITH SATURATED POLYURETHANE COVER Cover CompositionH₁₂MDI Prepolymer* 458.73 g  1,4-Butanediol 42.75 g HCC-19584 ColorDispersion** 17.55 g Physical Properties Cover Shore D Hardness 54 BallWeight (g) 45.58 Ball Compression 89 Cover Shear Resistance Good CoverColor Stability Comparable to Surlyn ® *Reaction product of4,4′-dicyclohexylmethane diisocyanate and PTMEG with Mw of 2,000. **Awhite-blue color dispersion manufactured by the PolyOne Corporation

These molded balls were compared to golf balls having aromaticpolyurethane or Surlyn® covers by subjecting them to a QUV test inaccordance with ASTM G 53-88 “Standard Practice for Operating Light andWater-Exposure Apparatus (Fluorescent UV-Condensation Type) for Exposureof Nonmetallic Materials.” Six balls of each variety were placed in golfball holders and placed into the sample rack of a Q-PANEL model OUV/SERAccelerated Weathering Tester (Q-Panel Lab Products of Cleveland, Ohio).Each ball at its closes point was about 1.75 inches away from an UVA-340bulb. The weathering tester was cycled every four hours betweenCondition 1 (UV on at irradiance power of 1.00 W/m²/nm, water bath 50°C.) and Condition 2 (UV off, water bath 40° C.). Color was measuredbefore weathering and after each time cycle using a BYK-Gardner ModelTCS II sphere type Spectrophotometer with a 25-mm port. A D65/10°illumination was used in specular reflectance included mode. Testresults are tabulated in Table 3, where ΔL* is difference inlight-to-dark dimension, Δa* is difference in red-to-green chromadimension, ΔC* is the combined chroma difference (a* and b*), ΔH* istotal hue difference (excluding effects of luminescence and saturation),ΔE* is total color difference, and ΔWI (ASTM E313) is difference inwhiteness index.

TABLE 2 UV STABILITY DATA Duration Sample Golf Balls ΔL* Δa* Δb* ΔC* ΔH*ΔE* ΔWI ΔYI 24 hours Aliphatic PU Cover −0.21 −0.30 1.54 −1.26 −0.941.58 −9.07 2.99 Aromatic PU Cover −17.27 11.36 46.14 47.31 4.36 50.56−142.35 93.80 Surlyn ® Cover −0.39 −0.25 0.91 −0.76 −0.55 1.02 −6.191.69 48 hours Aliphatic PU Cover −0.48 −0.37 2.54 −2.02 −1.59 2.61−15.16 4.98 Aromatic PU Cover −23.46 15.01 42.75 45.18 3.44 51.02−127.75 98.96 Surlyn ® Cover −0.54 −0.39 1.43 −1.18 −0.91 1.58 −9.502.66 120 hours  Aliphatic PU Cover −0.92 −0.46 5.87 −3.01 −5.06 5.96−33.72 11.68 Aromatic PU Cover −30.06 16.80 33.37 37.29 2.11 47.95−107.12 94.42 Surlyn ® Cover −0.99 −0.85 4.06 −2.91 −2.96 4.26 −24.887.73

Example 2 Diol-Cured Polyurea Cover

Golf balls were made having a polyurea cover comprising a prepolymer ofH₁₂MDI and polyoxyalkylene diamine (M_(w) 2,000), cured with1,4-butanediol. Properties and performance results in comparison withaliphatic polyurethane covered golf balls of Example 1 above are listedbelow.

TABLE 3 GOLF BALL WITH DIOL-CURED POLYUREA COVER Ball Properties Ex. 1Covered Ball Ex. 2 Covered Ball Compression 86 86 COR @ 125 ft/sec 0.8070.805 Cold Crack Test, 5° F. no failure no failure ΔYI (5 Days QUV) 3.20.8 Δb* (5 Days QUV) 1.7 0.4 Shear Test 3 2

Example 3 Diamine-Cured Polyurea Cover

Golf balls were made having a polyurea cover comprising a prepolymer ofH₁₂MDI and polyoxyalkylene diamine (M_(w) 2,000), cured with Clearlink®1000. Properties and performance results as compared to aliphaticpolyurethane covered golf balls of Example 1 are listed below.

TABLE 4 GOLF BALL WITH DIAMINE-CURED POLYUREA COVERProperties/Performance Ex. 1 Covered Ball Ex. 3 Covered Ball Compression89 92 COR @ 125 ft/s 0.807 0.815 Cold Crack at 5° F. no failure nofailure ΔYI (5 Days QUV) 4.3 0.6 Δb* (5 Days QUV) 2.4 0.3 Shear Test 3 1

Example 4 H₁₂MDI Amine-Terminated Compound Urea Cured with a Diamine

Golf balls were made having a polyurea cover comprising a prepolymer ofH₁₂MDI and amine-terminated polybutadiene, cured withN,N′-diisopropyl-isophorone diamine (Jefflink® 754 by HuntsmanCorporation). These balls, in comparison with aliphatic polyurethanecovered balls of Example 1 above, had better shear resistance, improvedlight stability, and higher COR.

Example 5 Moisture Resistance of Polyurethane-Covered Golf Balls

Golf balls were made having a cover comprising a prepolymer of MDI andhydroxy-terminated polybutadiene, cured with4,4′-bis(sec-butylamino)diphenylmethane (Unilink® 4200 by HuntsmanCorporation), and compared to aliphatic polyurethane covered golf ballsof Example 1 above. The covers were molded over wound cores of 1.58inches in diameter, and finished with a conventional coating. The golfballs were incubated at 50% relative humidity and 72° F. for one week,and then at 100% relative humidity and 72° F. for 7 weeks. Weight andsize gains at different time points are listed below.

TABLE 5 WEIGHT & SIZE GAINS IN POLYURETHANE-COVERED GOLF BALLS Balls 4days 1 week 12 days 18 days 3 weeks 4 weeks 5 weeks 7 weeks Ex. 1 +0.06g  +0.08 g  +0.09 g  +0.13 g  +0.13 g  +0.13 g  +0.15 g  +0.18 g Covered0 +0.001 in. +0.001 in. +0.001 in. +0.001 in. +0.001 in. +0.001 in.+0.001 in. Ex. 5 +0.01 g  +0.01 g  +0.01 g  +0.02 g  +0.02 g  +0.02 g +0.02 g  +0.03 g Covered 0 0 0 0 0 0 0 0

Example 6 Moisture Resistance of Polyurea-Covered Golf Balls

Golf balls were made having a solid core, an intermediate layer, and apolyurea cover comprising a prepolymer of H₁₂MDI and amine-terminatedpolybutadiene, cured with Unilink® 4200 and/or Jefflink® 754, andcompared to golf balls having the cover of Example 5 above, using thesame incubation procedure. The polyurea-covered golf balls had a weightgain of 75-80% less than the polyurethane-covered golf balls, and nosize gain after 7 weeks.

Example 7 Polyamide Polyurea Compositions

Golf balls were made having polyurea covers comprising prepolymers ofH₁₂MDI and diamino polyamides (reaction products of Jeffamine® D2000 andadipic acid or dimer diacid), cured with Clearlink® 1000. Properties andperformance results in comparison with aromatic polyurethane coveredcontrol golf balls are listed below.

TABLE 6 POLYAMIDE POLYUREA GOLF BALL COVERS Control Example 7A Example7B Formulations Isocyanate MDI H₁₂MDI H₁₂MDI Telechelic PTMEG withDiamino Diamino M_(w) of 2,000 Polyamide A¹ Polyamide B² CurativeEthacure ® 300³ Clearlink ® 1000 Clearlink ® 1000 Ball Diameter Pole1.682 1.689 1.688 (in.) Equator 1.682 1.685 1.684 Weight Average (oz.)1.610 1.608 1.603 Compression 84 85 85 Cover Shore C 80 77 78 HardnessShore D 59 56 58 COR @ 125 ft/s 0.810 0.808 0.806 Shear Test 1 3 2Durability @ 400 hits No failures No failures No failures Cold CrackTest @ 5° F., 15 hits No failures No failures No failures LightStability (8 Days QUV) Yellowing No Change No Change ¹Reaction productof Jeffamine ® D2000 and adipic acid. ²Reaction product of Jeffamine ®D2000 and Empol ® 1008 (dimer diacid from Monson of Leominster, MA).³Dimethylthiotoluene diamine from Albemarle Corporation of Baton Rouge,LA.

Golf balls were made having polyurea covers comprising prepolymers ofH₁₂MDI and diamino polyamides (reaction products of adipic acid andblends of Jeffamine® D400 and D2000), cured with 1.02 eq. of Clearlink®1000. Properties and performance results in comparison with aromaticpolyurethane covered control golf balls are listed below.

TABLE 7 POLYAMIDE POLYUREA GOLF BALL COVERS Control Example 7C Example7D Formulations Isocyanate MDI H₁₂MDI H₁₂MDI Telechelic PTMEG withDiamino Diamino M_(w) of 2,000 Polyamide C¹ Polyamide D² CurativeEthacure ® 300 Clearlink ® 1000 Clearlink 1000 Ball Diameter Pole 1.6831.686 1.685 (in.) Equator 1.683 1.683 1.683 Weight Average (oz.) 1.6091.599 1.600 Compression 87 89 90 Cover Shore C 82 86 84 Hardness Shore D58 62 60 Material Hardness (Shore D) 48 52 51 COR @ 125 ft/s 0.810 0.8080.808 Shear Test 1.2 4.8 6 Durability @ 400 hits No failures 1 failureNo failures Cold Crack Test @ 5° F., 15 hits No failures 4 cracked Nofailures Light Stability (8 Days QUV) Yellowing No Change No Change ¹60%D400, 40% D2000, % NCO 6.4%. ²40% D400, 60% D2000, % NCO 6.95%.

Example 8 Polyamide Polyurethane Compositions

Golf balls were made having polyurethane covers comprising prepolymersof H₁₂MDI and polyamide diol with caprolactone and 7% Desmophen® N,cured with Clearlink® 1000. Properties and performance results incomparison with aromatic polyurethane covered control golf balls arelisted below.

TABLE 8 POLYAMIDE POLYURETHANE GOLF BALL COVERS Control Example 8CFormulations Isocyanate MDI H₁₂MDI Telechelic PTMEG with Polyamide diolwith M_(w) of 2,000 caprolactone and 7% Desmophen ® N¹ CurativeEthacure ® 300 Clearlink ® 1000 Compression 87 89 Cover Shore C 82 84Hardness Shore D 59 60 Material Hardness (Shore D) 48 46 COR @ 125 ft/s0.808 0.806 Shear Test 1.5 2.7 Light Stability (8 Days QUV) Yellowing NoChange Durability @ 400 hits No failures No failures Cold Crack Test @5° F., No failures No failures 15 hits

Example 9 Aminoalcohol Telechelic Based Reactive Compositions

Golf balls were made having covers comprising prepolymers of uretdioneof HDI or H₁₂MDI and aminoalcohol telechelics, cured with Ethacure® 100LC or Clearlink® 1000. Properties and performance results in comparisonwith aromatic polyurethane covered control golf balls are listed below.

TABLE 9 AMINOALCOHOL TELECHIELIC BASED GOLF BALL COVERS Control Example8A Example 8B Formulations Isocyanate MDI Uretdione of HDI H₁₂MDITelechelic PTMEG with Aminoalcohol Aminoalcohol M_(w) of 2,000Telechelic A¹ Telechelic B² Curative Ethacure ® 300 Ethacure ® 100 LCClearlink ® 1000 Material Hardness (Shore D) 48 49 51 Compression 86 8788 COR @ 125 ft/s 0.807 0.808 0.809 Shear Test 2 2.2 2.8 Durability @400 hits No failures No failures No failures ΔYI (8 Days QUV) 65.2 25.61.7 Δb* (8 Days QUV) 24.9 14.5 0.9 ¹% NCO at 8.5%. ²% NCO at 7.5%.

Golf balls were made having covers comprising prepolymer (10% NCO) ofuretdione of HDI and aminoalcohol telechelics, cured with a blend of0.825 eq. Clearlink® 1000 and 0.125 eq. Desmophen® 1520 (from BayerCorp.). Properties and performance results in comparison with polyureacovered control golf balls are listed below.

TABLE 10 AMINOALCOHOL TELECHELIC BASED GOLF BALL COVERS Control Example8C Formulations Isocyanate H₁₂MDI Uretdione of HDI TelechelicPolyoxyalkylene Aminoalcohol diamine Telechelic C¹ (M_(w) of 2,000)Curative Clearlink ® 1000 Clearlink ® 1000 & Desmophen ® 1520Compression 90 93 Cover Shore C 84 90 Hardness Shore D 58 60 COR @ 125ft/s 0.805 0.805 Shear Test 2 1 ΔYI (8 Days QUV) 0.9 4.2 Δb* (8 DaysQUV) 0.5 2.4 Heat Resistance No cracks or wrinkles No cracks or wrinkles(8 Days QUV) ¹% NCO is 10%.

Example 10 Amorphous Polycarbonate Telechelic Based ReactiveCompositions

Golf balls were made having polyurethane covers comprising prepolymersof H₁₂MDI and amorphous polycarbonate polyols, cured with1,4-butanediol. Properties and performance results in comparison withpolyurea covered control golf balls are listed below.

TABLE 11 AMORPHOUS POLYCARBONATE TELECHELIC BASED GOLF BALL COVERSControl Example 8B Formulations Isocyanate H₁₂MDI H₁₂MDI TelechelicPolyoxyalkylene Poly(hexamethylene diamine carbonate-block- (M_(w) of2,000) trioxyethylene carbonate- block-hexamethylene carbonate) diolCurative 1,4-butanediol 1,4-butanediol Material Hardness 48 47 (Shore D)Compression 85 85 COR @ 125 ft/s 0.806 0.801 Shear Test 1 2 Durability @400 hits No failures No failures ΔYI (8 Days QUV) 0.8 1.2 Δb* (8 DaysQUV) 0.4 0.6

The forgoing disclosure and the claims below are not to be limited inscope by the illustrative examples presented herein. Any equivalentexamples are intended to be within the scope of this disclosure. Forexample, while disclosure is directed mainly to compositions for use ingolf balls, the same compositions may be used in other golf equipmentsuch as putters (e.g., as inserts or in the grip), golf clubs andportions thereof (e.g., heads, shafts, or grips), golf shoes andportions thereof, and golf bags and portions thereof. Indeed, variousmodifications of the disclosure in addition to those shown and describedherein will become apparent to those skilled in the art from theforegoing description. Such modifications are also intended to fallwithin the scope of the appended claims. Disclosures of relevant subjectmatters in all patents, applications, and publications as cited in theforegoing disclosure are expressly incorporate herein by reference intheir entirety.

1. A golf ball comprising a core, an inner cover layer, and an outercover layer, the outer cover layer being formed from a polyureacomprising: a prepolymer comprising: an aliphatic isocyanate; and asecondary polyamine polyether having a formula:

where x=1-70; R₁ and R₂ each independently=a C₁₋₂₀ alkyl group, phenyl,or a mixture thereof; and R₃═H, CH₃, or a mixture thereof; and an aminecurative.
 2. The golf ball of claim 1, wherein the amine curativecomprises 3,5-diethyl-2,4-toluenediamine or3,5-diethyl-2,6-toluenediamine.
 3. The golf ball of claim 1, wherein thealiphatic isocyanate comprises 2% by weight to 15% by weight reactableisocyanate moieties.
 4. The golf ball of claim 3, wherein the aliphaticisocyanate comprises 5% by weight to 11% by weight reactable isocyanatemoieties.
 5. The golf ball of claim 4, wherein the aliphatic isocyanatecomprises 6% by weight to 9.5% by weight reactable isocyanate moieties.6. The golf ball of claim 1, wherein the aliphatic isocyanate comprises1,6-hexamethylene diisocyanate.
 7. The golf ball of claim 1, wherein thealiphatic isocyanate comprises uretdione of hexamethylene diisocyanate8. The golf ball of claim 1, wherein the aliphatic isocyanate comprisesisocyanurate of hexamethylene diisocyanate
 9. The golf ball of claim 1,wherein the aliphatic isocyanate comprises dimerized uretdione ofhexamethylene diisocyanate, trimerized isocyanurate of hexamethylenediisocyanate, and trimerized biuret of hexamethylene diisocyanate. 10.The golf ball of claim 1, wherein the aliphatic isocyanate comprises2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, or4,4′-diphenylmethane diisocyanate.
 11. The golf ball of claim 1, whereinthe secondary polyamine polyether does not contain an —OH group.
 12. Thegolf ball of claim 1, wherein the core comprises a solid center and anouter core layer.
 13. The golf ball of claim 12, wherein the center hasan outer diameter of 0.095 inches to 1.1 inches.
 14. The golf ball ofclaim 1, wherein the outer cover layer has a material hardness of 70Shore C to 80 Shore C and a hardness, as measured on the golf ball, of40 Shore D to 55 Shore D.
 15. The golf ball of claim 1, wherein theouter cover layer has a first hardness and the inner cover layer has asecond hardness, and a ratio of the first to second hardness is 0.8 to0.7.
 16. The golf ball of claim 1, wherein the outer cover layer has athickness of 0.025 inches to 0.04 inches.
 17. The golf ball of claim 1,wherein the inner cover layer has a thickness of 0.01 inches to 0.045inches.
 18. The golf ball of claim 1, wherein the inner cover layer hasa thickness of 0.025 inches to 0.035 inches.
 19. The golf ball of claim1, wherein the core has an outer diameter of 1.5 inches to 1.6 inches.